On our machines, the C:\ drive is fast and small and the e:\ drive is the user directory, one thing that is quite hard is to make sure the various user files in c:\documents and settings move to e:\. You can do a simple thing which is to
Right click on the My Documents and then change them from c:\ to e:\, but this doesn't move any of the local settings like Outlook's gigantic directories or the IE cache.
Wes' Puzzling Blog : Moving XP User Profile. This tells you where the magical settings are. You can just copy c:\documents and settings to e:\documents and settings then go through each user directory in in HKEY_LOCAL_MACHINE\SOFTWARE\Microsoft\Windows NT\CurrentVersion\ProfileList. Double-click the ProfileImagePath subkey and replace its contents with e:\documents and settings\jake. Close your registry editor.