If you have experience in another language, and once you've gotten the Ruby syntax loaded into your brain (e.g. procs, lambdas, if/unless as a modifier, case statements, define a class, how optional parens work) I can recommend two options:

1. The Pickaxe Book (Programming Ruby by PragDave). You can read the book itself, but one thing I love is that it explains the entire stdlib in an appendix. I learned a lot just by keeping it near the bathroom and flipping through that appendix a few times each day.

2. POODR by Sandi Metz (referenced above) is about OO but you will also get a sense of how to write non-web, pure Ruby applications in a general sense.

Try The Well-Grounded Rubyist. I appreciate that it focuses on the language, not the standard library.

http://www.manning.com/black3/

Chris Pine's Learn to Program! It's a great book that both introduces coding concepts and Ruby really well.