1) I can change my ip address in less than 2 minutes. Legally
SteamID, not so much. I'd have to purchase a new account. (or, illegaly, one would have to hijack one)
Not sure why you think banning his IP will prevent him from connecting using a different one.
2) You're using rcon or server console for addip right?
One of the reasons ULX makes things so easy is because you can use it from game/client console, and it will run stuff on the server side.
If you're not using rcon or server console, that's likely why it's not working.
(and, make sure you're looking at banned_ip.cfg on your server, not your game (unless of course, you're running a listen server)
3) If #1 doesn't discourage you, and you're doing #2...what exactly are you typing and where?