I came from a Unity3D background as well as Papervision3D back in the day, so I had a good understanding of how to deal with 3D space. Three.js is the way to go for your initial jump into learning how to deal with WebGL projects. The api is very good, it's very powerful and if you're coming from another 3D technology, you'll be up and running with very little time.
I spent a lot of time with Threejs.org's examples - there's a ton of them and they're very good at getting you off and running in the right direction. The docs are decent enough, especially if you're comparing them to other webGL 3D api's out there.
You might also consider getting the free version of Unity3D and the free collada (was free when I got it) exporter from their app store (Window>App store). I found it easy enough to setup my scene in Unity and export it to Collada for use with Three.js.
Also, I posted this class that I use with Three.js called neo ( http://rockonflash.com/webGL/three/neo.js ). Just add it to your project, then call Neo.JackIntoThree() and it will add the methods/properties to Object3D for use in your project. Things like DrawAllAxis() are invaluable when debugging your scene etc.
Hands down though, Three.js is a great way to go - it's flexible enough to let you write your own shaders/objects etc, and powerful enough right out of the box to help you accomplish your goals.