I'm having a lot of fun with my Steam Controller. I'm yet to try analogue stick centric games, but have gone through dpad and mouse aim games along with fully mouse and keyboard centric strategy. The mouse stuff works great after about an hour with it, but passing the 4 hour mark I'm not at the point where I can headshot someone as fast as I'd like, and I suspect it would take a lot longer for me to get there.
Dpad wise, with the right settings it is a pleasant surprise. Spelunky and Shovel knight all play brilliantly. However I have to have a very specific deadzone set up and haptics turned way up so I can understand whats going on, in a much better way than I have on the ds3 and 360 pads. Even MK9 worked out well with this set up, doing all the fatalities and moves in succession, but it feel weird still. Binding of Isaac is broken for whatever reason, which is a big disappointment.
Hands down the best thing so far is mouse driven games like Civ V. A damn joy to play.