WSS stores user information in the UserInfo table in each content database.
MOSS uses both the UserInfo table and user profiles in the SSP. The attributes
of a user are copied to the Userinfo table when a user first accesses a
SharePoint site. After that if you are using WSS the only way to update
attributes like email is to edit the record directly, which can be done either
by the administrator or the user. If you are using MOSS, then the user profiles
can be setup to run a recurring import of information. This will update most
fields in the user profile including the email address. (Note: Some fields like
Display name don't update appropriately). Changes to the User Profiles are then
synced with the userinfo table by a timer job that should run every hour, but
I've seen it take a day or so before the change comes through. Since, the email
address that users see when they click on a user is the one stored in the
Userinfo table you need to wait for a substantial time before the change
replicates through the system. You also need to have Profile Imports running to
pull the change in from AD.