A few options.
TGT Soft offers a program that lets you use any of the .theme files found on the Internet. That's the safest way, but it's not freeware. The free way involves using a patched/hacked uxtheme.dll file (that's the file that generates the actual theme from the .theme file). That can be found on many websites, but
neowin has made a
UXTheme Multi-Patcher that will usually do everything automatically. If you have SP2 installed though, you'll have to do it manually as well as find the uxtheme.dll file specifically for your build of SP2, as each build of windows requires a different version of uxtheme.dll (that's why Neowin made the Multi-Patcher).
Also,
Stardock makes
WindowsBlinds which is an alternative to the MS theme engine. Not only do they charge for it, but it uses more system resources. I personally wouldn't go with this.
Hope you enjoy the world of themes. I'll never go back to Luna (the default XP theme) on my desktop.
BTW, here's my desktop from a few days ago:
edit: just re-read your post...hmm, when new users log on, get the custom theme. Just thinking outside the box here, but you may need to replace the Luna theme with the custom one you choose. By default, Windows will load the Luna file, so I guess you can trick it by renaming the custom theme to Luna, but that's a little risky. BTW, themse are located in C:\WINDOWS\Resources\Themes.