Most rooms wont let you play if your on the same network like someone said.
I don't know if any rooms allow hold em one on one because they make a little bit of money on each game played and not many people want one on one rooms so I think it will be hard even getting a paid 1 on 1 room.
Why dont you just go to a room with a lot of free tables and find one that doesn't have any players on it?
I'm playing on www.PaddyPowerPoker.com
right now and theres about 8 tables with no players in them.