Eclipse 3.x
The learning curve for Eclipse development in general is quite steep indeed, no matter if you are developing plug-ins or standalone RCP applications. The Eclipse Plug-ins (3rd Edition) book mentioned in zedoo's answer is a very good starting point for understanding the underlying concepts and APIs of the Eclipse 3.x stream.
As far as online resources go, Lars Vogel has lots of very detailed and useful tutorials on his website for RCP deleopment and Eclipse plug-in development in general.
e4
The Eclipse 4.0 SDK Early Adopter Release main page has links to a couple of tutorials and a very detailed release notes, and most importantly a new & noteworthy page with all the shiny new features compared to the 3.x stream.
Conclusion
Of course e4 is still not as mature as Eclipse 3.6, the latest release in the 3.x stream, which is clearly a downside. However, as far as I can see after playing around with it recently, the APIs and the whole development methodology have been streamlined, which makes it easier to get up and running. Documentation is still a bit sparse, but new tutorials and blog posts keep popping up frequently and there is more and more buzz around e4 in general.
Starting directly with e4 would save you the trouble of learning and eventually unlearning the 3.x API, so if you are in it for the long run, I would say go for e4 now.
If this is just a relatively short one-off project and you want to reduce the risk, then go for 3.x and reap the benefits of the mature code base and lots of documentation.