Did something like this to move to a new NT4 domain a few years ago - what we did was rename the existing user profile directories - although new users were being created in the destination domain in this example, so that there were no SID conflicts.
We renamed the existing Default User profile to Default Old and renamed the existing user's profile to Default User. Then when the user logged in with their new user account in the new domain, their profile was created with all the settings (wallpapers, favourites, cookies, printers, etc) that were in their old profile.
Alternatively these days there are a few tools that do this sort of thing - doesn't Microsoft provide a User State Migration Tool (USMT) to do this kind of thing?
Anyway, that's an idea for you - it worked smoothly enough for us, I recall.
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