Start with blogs and documentation. The blogs feature step-by-step tutorials on a variety of examples that you can build. Additionally, start with the Videos produced by VMware's Education department:
http://www.vcoteam.info/learn-vco/free-vmware-vcenter-orchestrator-instructional-videos.html
Blogs: see Joerg's post here: http://communities.vmware.com/message/2181182#2181182
Good luck 