It is generally *NOT* safe to delete the User Library (~/Library) because it also holds user data for a number of applications like Address Book, iCal and Mail. If you delete their user library, you risk deleting emails that have been removed from the server and saved in a local folder, all their contact records, etc.
You could use network home folders or redirection, but regardless of where the user library is stored, you probably want to back it up.