I haven't switched to Homebrew but the advantage is that MacPorts creates its own universe of libraries, whereas Homebrew uses what Mac OS X already comes with. This makes installs a lot faster.
MacPorts creates it's own universe because that's the only reliable way to do it. What will Homebrew do when Python gets updated by Apple, or when you want 2.6.10 and Apple only has 2.6.4? With Macports the situation is easily dealt with, with Homebrew it's not.
"brew install python" works (and I've used it). In fact, I have a small pile of additional recipes locally for just doing custom, well-controlled compiles of Python.
And yet the recommended solution for upgrading MacPorts with an OS X upgrade? Uninstall and reinstall all ports. What's the point of it creating its own universe if it needs to destroy it anyways?