Python 3 is a great place to start for those "with no baggage" (meaning no existing Python code or apps, no libraries/dependencies that haven't been ported to Python 3 yet, etc.).
However on the other hand, although Python 3 is here, most of the industrial world still runs on Python 2, so if you do need to create an app to run today using the libraries and packages available to you, that's where you should start. If you do, use any release 2.6 or newer as they have features backported from 3.x to help you start thinking in a 3.x kind of way. :-) If you learn one, it's easy to adapt to the other (and vice versa).
On a related note, I had the publishers add two new appendices (C & D) to the latest printing (5th!!) of my book, Core Python Programming, one on Python 3.x and the other on the importance of 2.6 and the role it plays in helping users to transition to Python 3.
Finally, I've been giving talks on Python 3 and covering the main differences from Python 2. Here's one that I gave a PyCon a few months ago which includes the slide preso.