If you are new, I suggest RoR, since, it takes all the nitty griddy details out of the way, and lets you focus on the real outcome of your app. Take a Ruby Crash Course and jump into Rails.
Probably, I will start with RoR, at least it seems so now. :)
If that's the route you're going, I highly suggest Michael Hartl's Ruby on Rails Tutorial. The entire text is available for free, but you can pay for a PDF version and accompanying screencasts.