Hello, and welcome on board!
I have this software combination too, and I really like it.
If you are doing a lot of 2.5D work, cutting sheets etc, I hope you have Rhinocam2 because of the bridge function.
The best way to learn (besides getting a local tutor) is by starting with some small projects, and follow tutorials. The help menus are a great resource for both programs.
Rhinocam is the same as Visualmill, so any information from that side is also useful.
What type of of work are you looking at, and what cad-experience do you have?