I have always found it easiest to scratch a personal itch when learning a new language. One of the first things I wrote was a shopping list program for my wife. It was a pretty good way to start learning the lay of the python libraries - it needed a small object database, a gui (tk, although I far prefer wx at this point), and I generated HTML pages for printing out the lists. Good architecture? no. good to learn the lay of the land yes. Ask your friends/family - everybody has one thing they wish the computer would do. Not only will you learn python, but you'll help your friends.
As far as employment. I come from a java background, and that seems the only language I can pay the bills with:). Particularly in the US - paid python jobs are hard to come by. I have been able to scrape some side income doing zope/plone development for small businesses in the area wanting to create a web presence - ok so it's only a little bit of python and bunch of TAL/DTML. If you want to make money with python skills, I would recommend learning a python based web/app server, ie (Zope, cheetah, twisted) and look for small businesses needing websites. They frequently could care less about implementation choices, and it sounds like you have some experience in that field. -- http://mail.python.org/mailman/listinfo/python-list
