There is a wealth of on-demand and live training available at the MVA web site: (www.MicrosoftVirtualAcademy.com)
Now there is free on-demand App-V 5 Training featuring Ron Dockery and yours truly!
For the IT Pro that is either new to App-V or specifically new to App-V 5, this training should be a good introduction and deep dive into the App-V 5 management and publishing system. I hope you enjoy it and would love to hear suggestions for additional courses (Yes, one with Config Manager integration is likely in the works! :) )