I don't think Mike was outshining her in any way - her job sounds like it was one where she was still going to be making the bulk of the money for the forseeable future - Mike sounds like he was starting at a fairly base level (that's what $12 an hour says to me - you're not in the executive club with that income), and may move up a little soon - but he probably won't be big enough in that company for many years (plus, it didn't sound like he had a college education, like his friend, who got him the job, which could be a hurdle to get over for a "good" job at the company).
That said, I think she needed to get her head straight a bit, too. She should have really left Mike a long time ago, especially if she knew that he was still using, and drinking like crazy. She was making herself better, and he was still acting immature - had she REALLY known what she wanted, she'd have left him in the dust a ways back. But she even alluded to it herself, when she mentioned to Mike for a second, that she wasn't able to hang out and party anymore. She was living between two worlds, and I don't think even she knew what she REALLY wanted, aside from maybe wanting to remove the temptation from her own life - thus making Mike try to shape up.
I think she got mad, because Mike getting the job after she "broke up" with him, seemed to her like it takes that kind of blowup to get him to do anything right. Almost like, he wouldn't do it, unless he knew that she was going to do something major. That can be very irritating in a relationship, if you always have to push people to the edge before they do something positive. Mike was one of those guys - even the very end of the movie was proof of that - he needed Jim to show him extreme violence and insanity for him to realize that he didn't want his life to be that way anymore. Him crying to Sylvia at the end, I think, was symbolic of him turning a corner and being ready to start a more normal life.
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