First thing you want to do is check out the
man page for the command crontab(1) and the
file format for crontab(5).
You need to edit the user's (say Joe) crontab by:
crontab -u joe -e
...the make your entry. By the way, the editor
will be either "vi" or whatever you EDITOR
env. variable is set to. The man page for the
file format should show you exactly how to make
an entry to get what you want (I don't want to
give it away

) and you save it.
just an example:
# run at 10 pm on weekdays, annoy Joe
0 22 * * 1-5 mail -s "It's 10pm" joe%Joe,%%HI JOE!!!%