After spending quite a lot of time developing 3D I came to realize that in most cases the best way is to learn by examples and advance with them as you go.
Start by setting to yourself a goal to achieve (for example - implementing a particles system. this includes usage of blending modes, textures, vertex colors, batching and transformations), and then go and start with the simplest element - drawing and rotating a quad. From there go on and add textures, add more quads, etc...
While doing that you'd need some info about the syntax - this you can find in many books, but the best (very boring) source is the specification committee publication that can be found here: http://www.khronos.org/opengles/spec/
Even with that you'd bump into many problems, well, once you have a problem go to your best friend in these situations: demos and examples!
You can find many examples sources for the iPhone online and at the apple site so download them, copy paste what you need and then alter to your needs.
Have fun.