If it is just for a set of existing users, I'd add them in lowercase, then edit /etc/passwd /etc/shadow /etc/group /etc/gshadow and mv the /home/ directory to names you want (making sure everything matches).
You might choose to use vipw and vigr to edit the above files as well.
If you use local mail spools, you will need to rename /var/spool/mail/user to /var/spool/mail/USER
Barry