If you want control over your UV Maps and to get useful UV Mapping tools, Hexagon 2.5 comes with a decent UVMapper. Hexagon is still available for free. I would recommend it as you do have full control.
Here is a basic UVMapping tutorial I wrote for it:
That one only really goes through its auto-UV mapper. However, this 3D tutorial includes auto-UVMapping BUT shows you how you can then customise the UV Map for the best results in the UV editor.
Then there is a more complicated method, which is useful for UV Mapping characters, especially heads, but I've not written a Hexagon tutorial for it yet, but if you learn how the Unwrap mode works all you need to do is imitate what I did in this video tutorial:
(Sadly this was done with the trial of this program, I would love a copy of the full version
Interestingly, the only video tutorial I've written, I should attempt more - though I sound really camp in that video.
I use the same method in Hexagon, so it should work. Hexagon has a couple of extra options, so you might have to fiddle around with them (such as Projection Axis (X, Y or Z)) to get the best result. In some cases you may have to jump into the UV editor and make your own adjustments.
Generally with a UV Map you'll want the faces you want to pain on exposed and in a fashion where they do not over lap and in a layout where you can see where you're painting and the resolution is fairly consistent on the faces.
I used to find Lithunwrap was able to do what I wanted with tweaking, but the awesome thing with Hexagon's UV Mapper is you've got more options and more control and of course some more conveniences (like selecting edges/faces/points in your 3D window)