Cetaganda was the first book in the Miles series I read (as part of Miles, Mystery & Mayham omnibus), and while I really enjoyed it - like a LOT, laughing out loud many times, and actually reading several scenes to my sister - it didn't pull me into a Bujold reading binge. That happened a year later, once I started the series from the very beginning.

I know that Cetaganda was one of the later books written, and it shows - it's more finessed than the earlier ones. But I wouldn't start the series here, and I think I would appreciate it more once I was already familiar with the characters.