This Ruby tutorial is great for those who are new to programming. True to its title, it is difficult yet effective. It teaches the very basics of programming, which is essentially trial and error. I suggest this book for anyone looking to learn how to program outside of a browser.
Codecademy is a good resource. It is a great way to get acclimated to programming syntax. However, eventually, the student will want to take the "training wheels off" and work in an actual web dev environment.
Learning Ruby the Hard Way would be a logical step if the student is interested in the next level. It will also teach the student the very basics of setting up a dev environment.