Safest way in my books would be to start safe mode and log in with a different user. Take a complete copy of the user profile, c:\documents and settings\username... then go to system properties and leave the domain.
You can now restore the users documents and settings to wherever they need to be. I am not really sure of any easier way that is safe.
You may want to try the user migration tools (Windows Easy Transfer for XP), but I am unsure if this works on a domain.
Personally, if this was me, I would do the above backup first and then just reinstall from scratch. If it has been on a domain, it is likely that there may be settings left behind that can bite you in the a$$ later when you are wondering why something isn't working.