I put extremis first.
I think that's more defining, because it starts with the interview about his actions in the (then) middle-east and how he's trying to move past them, and his minor rationalizations
It also shows him pushing the boundaries of his technology with the extremis virus
It also cuts to the crux of his character, using technology for good vs bad like malen.
It's still somewhat poorly developed in terms of malen and the deal with maya, but on the whole it's a good microcosm or defining story.
Demon in the bottle didn't really stick with me that much. For his alcoholism story, the stane one was better. For one it was more drawn ou. The actual demoning in the bottle lasted only 2 issues minus the build up. The relationships were better explored like with rhodey and cap.