As a precaution, why not change the location of the existing switch, and wire the new switch through that - so the existing switch acts as a breaker - you can leave it off while fitting the new switch and reduce the risk of death.
The worst thing I've done with electricity, is mess around with a camera flash capacitor, damn thing nearly took my finger off. I did it again only a year or so ago - changing an LCD screen in a camera, didn't discharge it, and touched the capacitor contacts.
That's the sort of stuff that gets you - it's not direct current, it's the high amp, stored stuff like capacitors and coils that can seriously hurt you - and the charge tends to be held for ages after you unplug. It's amazing that something that works on 3v batteries can hurt like that, and I used to lick 9v batteries for kicks so I'm no wuss when it comes to shocks.
I say don't open the PSU, wire it through the existing switch - if the original switch is on the PSU and you'd have to open it up to get at it, then leave it alone. You might well burn out that PSU anyway, so you really want it to be easily replacable.

Health, Ammo, and bacon and eggs!
