WezzLee,
There is not much you can do, since we need to see where in the process it rejects procasters hooking and how to circumvent this.
You could send us in your logs (Preferences --> Video --> Save logs, then they are on your desktop) to
procaster@livestream.com for some debugging information, but that would probably not resolve the issue with Dota 2. Most of the time they introduce some anti cheating mechanism that in turn also blocks procaster.