Went to lunch last week with a old friend from Pactitle. We were a Shake house; this was before Nuke was for sale to the public.
Walking back from lunch he asked a question
"What are the important things to be good at with Nuke".
Tom, you asked a very complex question. Some would argue the channel system, some would say the mock 3D world. Others would say just straight 2d comp. Its not the RotoPaint node that's for sure. Here are some ideas and links. Enjoy.
Layers and Channels
So much flexibility can be found in layers and channels. Not to mention cleaner more readable scripts. Which is always a good thing. Having your mattes and other images down stream from you is great. Here is a link to the nukepedia article about the subject.
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Most of this is learned from Josh Johnson. He was and should still be the lead Roto/Paint artist at Digital Domain. Shuffle a white alpha before you start painting if you need to use the onion skin feature. This is not a fail safe. but it helps. Get good at paint in Nuke it will get you out of some bad rock and a hard place type of situations.
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If you have access to NukeX then get good the Camera Tracker. At least as good as you are with the 2d tracker. So much data you can get for free if you have a camera for the shot. Pointsto3d is amazing node. Aleast makes up for the shit paint in Nuke.
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Yeah I know programing languages. Boring! It can make your life easier. Even if you just copy and paste other peoples Python[OPP] it can help. Python for Artists