[]all I see there is username and IP address with the % thing[/]
You should be able to ban his IP address. You mentioned that he is using several different ones. In our experience, the only ones that really prove to be a problem are 1.) AOL, because they route half the country through the same IP's, or 2.) You have several members in a very small area sharing the same line and therefore the same IP (like in the same neighborhood, small city, etc.) Other than those two circumstances, we haven't had a problem banning IP's.
Run a search like this:
SELECT DISTINCT B_ip FROM w3t_Posts WHERE B_Username = ' [:"red"]username[/] ' (enter their username)
and then this:
SELECT B_Username FROM w3t_Posts WHERE B_ip LIKE '[:"red"]XXX.XXX.XXX.XXX[/]' (enter each of the IP's you got from the first search)
The first search will give you all the IP's he's posted under. Then the second search will tell you if anyone else has posted with those IP's other than him. If you don't have any conflicts, ban those IP's. We usually try taking the IP back a few digits if all of their IP's are similar, using '%'
If you find that his IP or IP's will be easy to ban and not conflict with other users, you can add the IP to an .htaccess file and deny him access to your entire site. (I think your server needs to be running Apache to use the .htaccess?) With certain users we ban their IP and then we deny them access to the site totally. We've only had 1 person in 40 or 50 that went beyond that step and went to a library to sign up again.
We manually approve all users though, so she was caught before getting approved.
I adjusted those searches for what I could remember of the older versions (we're running 6.2.2). I think those are the correct ones though - the B_IP and B_Username from the Posts table.