In my experience, your safest bet would be to try a Sysprep, then ghost yourself a master image.
Sysprep will make your xp install like you just installed xp off a cd, but leave all the files intact. I would suggest the following:
Install windows (10gb partitino max is fine, i've used 6gb partition for xp with no sweat) and set it up as you'd like, with an arcade user login.
Put your roms, emulators, front-end, etc. on a seperate partition.
Overwrite the default user folder in documents and settings with your custom arcade user folder.
Sysprep with mini-setup and reseal.
Before your computer boots in to windows, ghost the windows partition.
Now on new installs, you just dump your partition image to the new hard drive, run the windows mini-setup, and create a user profile.
The old arcade user profile will be replacing the default user profile, so things should look exactly like the old profile. It'll take only 15 minutes to do a full setup/restore. All that's left is to copy your rom/emu/fe drive and you're set.
The attraction to sysprep is that it will let windows setup install all the drivers, and you can specify a folder during the sysprep.ini to grab new drivers from, if you feel so inclined.