I've been approaching this issue from the other end, by using Robocopy (available for free as part of the Windows 2003 Resource kit, here:
http://tinyurl.com/4k28b and works well on XP) as a scheduled task.
I'm also using the free pfbackup utility, also available from Microsoft, and setting that to back up the pst file(s) to a folder within the My Documents hierarchy so I don't have to back up the pst separately.
You can automate the procedure with a startup or scheduled script that references the %userprofile% and %username% environment variables. For instance, let's assume you have a server drive s: and a folder named backups.
robocopy "%userprofile%\desktop" "s:\backups\%username%\desktop" /XF *.lnk /MIR
robocopy "%userprofile%\my documents" "s:\backups\%username%\documents" /MIR
This will copy all desktop items excluding shortcuts and system icons (because you know how users like to keep files & folders on their desktops ...) and the entire My Documents hierarchy.
Backuppc would be a better solution for keeping versions of files, but I've not made the time to delve into its mysteries yet.