If you want a more "guided" approach to Python webdev, try looking into Django. There's a large community that has built up around it contributing tons of plugins.
I say this as someone who is working on a Pylons site. You can do anything with Pylons that is possible with Python, you just have to figure it out yourself or twist someone else's library to make it work. Sometimes you don't need that much freedom and the guided approach will do 90% of what you need. Do a bit of research and see which approach best suits your needs.
I'd also recommend a look at Flask: http://flask.pocoo.org/. It's quite new but more polished and easier to learn than Pylons, and comes with excellent documentation and handy extensions.
As you say, however, Django is a good place to start for a beginner - it has a larger community and ecosystem of apps for doing just about anything web-related (although the apps are of variable quality). It's also quite mature (5 years now) and has more job opportunities.
I say this as someone who is working on a Pylons site. You can do anything with Pylons that is possible with Python, you just have to figure it out yourself or twist someone else's library to make it work. Sometimes you don't need that much freedom and the guided approach will do 90% of what you need. Do a bit of research and see which approach best suits your needs.