It's a tricky one, because each company has different requirements, all I could really do is explain how the IT was put together here (at my work).
When I started we had 4 PC's on a network, there were about 20 email addresses, but only accessible on a PC in the hallway!, which also doubled up as an internet PC. We're only talking 2001 here

- now there's around 120 PC's, most networked, most have email and internet access.
Anyhoo...
Network:
The first order of business should be your servers. You need a domain controller, although this does not need to be it's own server, it should be one with a low overhead. Here we use the email server as a domain controller - as when you add a new user, the email stuff for MS Exchange is all there too, nice and easy to set up new users with a domain and MS Exchange. You can also setup a server to be a backup domain controller. We use a database server as well, holds all the shared data and applications. This acts as a secondary domain controller in case the other server is down.
So you need a server to hold all the company files, a server to hold all the company email, and if you use SQL or another heavy package like that (accounts package, SAP, MRP maybe) then I strongly advise getting a server for that as well.
For networking, I just keep it cheap - Cat5e cables everywhere, with 48 port routers in a rack, and servers and routers linked with the fastest ports. Often you'll get 2 or 4 high speed ports for linking routers together or high demand servers.
Hardware:
When buying supplies, printers etc I tend to leave a lot of it upto the purchasing department. I will source a suitable product, and raise an order for it - then it's purchasings job to find a better price, arrange discount, and actually place the order. Before very long you would find a good supplier for stuff and the process gets quicker and quicker - but just be aware that there are other departments who should be helping. The style these days is to have a smaller IT team that are easy to hold onto IMO, at least in these times - a lot of companies have gotten rid of IT people and then suffered. For instance a company we deal with visited myself to discuss linking our systems as we are a major supplier to them, they like to see everything that is happening. Anyway they kept going on about how strange it was for us to have just 1 IT guy. That was about a year ago, and they have since let about 80% of their IT team go, and they've left themselves open to issue all over the place without even realizing. Just thought I'd bring this up if you've got some slim hope of being supported with staff anytime soon, I think you have to stretch yourself as far as you can go, there's really no other way.
For PC's themselves I would say that standardization is vital. If you have 10 people with similar needs, get them the same identical PC. That way you have 1 recovery disk to keep track of, same goes for driver copies, if one of the PC's dies then it's ready for spares for the rest. It can save a lot of time and trouble to choose a brand and stick with it - you have all of 2 options at the end of the day... HP or Dell. I'd say that budget HP laptops were a bit better than Dell equivalents, but higher end Dell machines will be cheaper than HP.
For printers, well always look to the ink cartridges for justification. Another example... I bought a printer for the shipping department, has to be able to scan, copy, as well as print, and it has to be a mono-laser as well. So I picked one that was reasonably cheap, the toner was a bit small, half size in fact, so we'd use twice as much. Twice now I've been told to order a different printer that doesn't use so much ink. But, as I keep explaining to them, half size toner cartridges that cost half the price are gonna be replaced twice as much!. I found a replacement that would start to save us £14 per month, but only after 7 years, by which time any printer would have been replaced

. Some people just won't be told.
Software:
There are several email providers, small companies that provide IT and WEB services as well - you should speak with them about providing a clean and safe email feed, perhaps even charge them with the responsibility of providing and setting up the email server. It's not cheap, but it's efficient and holds benefits that I won't bore you with here. Exchange is very easy to install email accounts both locally and on the server. Other email solutions would probably force you to know a decent amount about email.
Virus protection is very important, find a reseller and buy licences for each PC, server, and each PC your company may buy in the comming year. I suggest sticking to year long contracts, if your virus protection of choice slips then don't be afraid of swapping it. I opted for Kaspersky here, which I have to say is doing an excellent job, it leaves most of your PC for you, unlike some other virus protection softwares.
Licensing things like MS Office is something I think best done through another company, like your email really - in fact our email server contractors also look after our MS licensing agreements and updates. MS Licensing is an animal, a big annoying, scary animal that only survives by being too complex for mortal men - MS licensing is actually a career in it's own. So leave it to people who know the system well, or get some really good training.
When it comes to ordering software or hardware, I tend to speak to managers - it can be risky to go ahead and give people just what they want without question. If someone asks for a new mouse then you should have lots in stores so it's no biggie, if someone asks for a new PC then that's something for their manager to decide. It can be troublesome to interject IT concerns into managers meetings, but finding out what is in the pipeline can really save time. If you think someone is needing a new PC, or if there's a new employee starting, try and get the information by yourself - never sit around and wait on them coming to see you. Thing is, most people will blame the next available person - and if your not on the ball then it could appear to some that you have an attitude even when you clearly don't. Don't let other managers dump on you, if someone checks up, like a managing director, then explain clearly what you need to get things done, what details your missing, without being negative, then it goes a long way. If an MD asks someone what is happening with their new employee's PC, then don't let it be waiting on you. I find having some spares is important, but regimented spares if you know what I mean. Try not to throw anything out, try and have a spare for emergency replacement as well as a spare for new employees.
Other useful things for IT guys to know is the health and safety stuff regarding working conditions and safety for office workers. It's all easy to pick up, but it can go a long way to just offer a little advice to make things more comfortable, ask people if they ever have headaches and neck pain. Also hand out wrist protectors and those gel mouse pads to people who are using the PC more than half the time. Foot rests and gel pads don't cost a lot of money but can make a big difference.
Damn this is a long post, but just to wrap up I'd say that things are very skewed in IT. You might think your doing the most important thing to the company, and you'd probably be right - but that doesn't mean a MD won't roast you for not checking his spam or something minuscule like that. And there's little point explaining, because the MD is like everyone else and has little interest in what is causing the problem or what will fix it - they just want you to shut up and fix it and let them back at their work.
You need thick skin sometimes, and you definitely need to know how to bite your lip, but if you work for a decent company then it is quite enjoyable at the end of the day.