The first command to type in Single User Mode (not Safe Mode, and hold command+s at startup to get into it) is "/sbin/mount -uw /" - that will let you actually modify the hard drive. Then, the basic commands you will need are these:
"pwd" - show which directory you are in
"cd" - change directory, using either the full path or relative to where you are
"ls" - list the files in the current directory
"ls -la | less" - list the files in a format that lets you scroll up and down
"rm" - remove a file
"cat" - view the contents of a file
"mv" - move a file to somewhere else.
An example of what you might do:
> /sbin/mount/ -uw /
> pwd
/home/users/whatever
> cd Library/Preferences
> ls -la | less
(long list of prefs files)
> rm com.apple.thepreferencethathasbeenscrewingeverythi ngup.plist
And finally..
> sync
> reboot
..which forces your changes to be written to disk and restarts. Alternatively, you could just type "exit" which attempts to take the system multiuser...
As a more drastic attempt, you could move his entire Library directory so that he could at least log in and debug stuff;
> cd ~
> mv Library Library.old