She always seemed to be flighty and self-absorbed. Her obsession with shopping being a prime example. At least that was the impression I got about her from the older eps, and the way she was "reintroduced" in this ep seemed to reinforce that. Prior to Monday's ep, it wasn't far-fetched to assume that she had an affair because Castle didn't pay enough attention to her. That is, sadly, a common reason for affairs, and her preoccupation with herself would lead one to that assumption.
So when she said that the marriage fell apart because she felt like she couldn't get Castle to open up to her, despite her opening up to him, it just seemed way out of character for her. It was a mature and thoughtful statement--one that I would have expected from his *second* wife, not from his first. The second wife being the editor or publisher or whatever she is struck me as being more intelligent than the first shopoholic wife.