I had never modeled before, and decided to start with
Blender because it's free and powerful. That is, there's no cost to try it out, and you'll probably never need anything else.
The learning curve is steep. Still, I was able to go through the
Blender: Noob to Pro tutorials and learned what I needed from those, plus fanatically reading the Forum here. I paid a lot of attention to the typical problems people were having (non-manifold, thin walls) and tried to view Blender through that lens.
It took a few weeks to really become comfortable. I had a fairly complex
project that motivated me. Now, as promised by the tutorials, I often wish that other applications worked like Blender.
I've never regretted the choice, and have many
complex prints to show for it. Blender is a very Shapeways-friendly environment, complete with
tools developed specifically for Shapeways to check models and compute prices. Shapeways' new
rendering environment is also done in Blender.
Hope this helps!