I believe I started with Beginning Ruby: From Novice to Professional by Peter Cooper. I liked The Well Grounded Rubyist and I've heard Eloquent Ruby is also good. Design Patterns in Ruby is less about ruby and more about design patterns, but still a good read.

I learned a lot about Rails from Michael Hartl's Ruby on Rails Tutorial book.

I learned the most through doing, though. I would work on building my own website and looked up anything I didn't know.