Each is the top of its respective line. S&W shooters favor the 27. Colt shooters favor the Python. I own both and like both just fine. I have more 27s than Pythons but if the Colts weren't so damned expensive I would have a couple more of them.
As nice as the 27 is the Python clearly outshines it in fit and finish. The Python was largely hand fitted and polished as opposed to the mostly assembly line production of the 27. The bad part is when you want to swap parts. In my experience two N frames will trade hammers and triggers about 95% of the time with no fitting required. Forget it with a Python. Hell, the stocks were individually sanded to each gun's frame meaning the wood will seldom swap between guns. Installing replacement stocks on a Colt can be a real adventure.
Love the 27:
Love the Python: