What I can assure you is that GKSession is very unstable and you should not trust these docs. In fact, Apple recently decided to remove the documentation altogether.
I did a lot of testing and I would suggest that the practical limit is 4 connected devices (one acting as a server and 3 clients). Of course it's better that you do your own testing scenario.
I also couldn't find any game that allows more than 4 players. The only that I knew was Apple own Texas Hold'em - which allowed 8 players, but they decided to remove it.
And last, but not least, Game Center imposes a 4 player limit to peer-to-peer games.
Yes I'm developing a game that should support 10 players but, in our tests, it became unstable/unusable when there were more than 4 devices. By unstable I mean: sometimes you can't find a peer and connection drops in less than a minute. To make matters worse, updating to iOS 6 brought some strange behaviors like freezing (no error, no stack trace, no nothing) while trying to send a message. Other odd thing: when a player loses connection, all other players get disconnected.
EDIT: did a lot of testing since that response and have more information to share:
Using iOS 6 I was able to play reliably with 9 devices using either wi-fi or bluetooth. There's stil a huge issue although: You can't connect devices using iOS 6 with devices using iOS 5 cause you will face unexplainable freezing-with-no-stack-trace time to time if any of the devices is with its wi-fi enabled. You either set iOS 6 as the minimum supported version for your App or you will have to ask users to disable their wi-fi and use bluetooth.