So I'm looking at the Steam sale and thinking to myself "hey, how convenient would it be to have a completely separate and clean Skyrim install to do CK work in?", but before I plonk down ￡23 for a second copy, I want to make sure this is possible. I know it won't work for the same user, because it's not possible as far as I can tell to select the location where your saves and ini files go(thanks, Steam! &--#62;:/ ), so both would end up looking in Documents\My Games\Skyrim, but would it be possible if I set up a new Steam account, a new Windows user account, and then installed Steam and Skyrim to the new Windows user?

I'm pretty sure that would work as long as select "install only for this user" when I install Steam, but if someone else has already done this successfully and can confirm it that'd be great.

EDIT: OK, nevermind, that idea didn't work, you can't even install two copies of Steam let alone Skyrim. Can anyone think of a workaround here?

There is no need, I think.
You can easily switch between two installs, if you want.

Install your first copy.
Suppose it goes into D:\Steam\steamapps\common\skyrim.
Now go to that folder.
Rename the skyrim folder to something else: e.g. skyrim.play

Now install Skyrim again.
Steam (or the dvd install utility) should notice that the skyrim folder is gone.
It should just reinstall a fresh copy of the whole skyrim game.

Now you have 2 installs in D:\Steam\steamapps\common, skyrim and skyrim.play

Whenever you want to switch, just rename the folders, so the one you want is called simply "skyrim", and start the game.

If you need separate ini-files and saves files, you could do the same thing with the My Documents\My Games\skyrim folder.
You could make a simple old-fashioned batchfile to rename the folder with one click.

I haven't tried this exactly myself though. But I've done something similar early this year.
I think it will be easier than making Steam believe you got 2 copies of Skyrim.