I've been hesitant to suggest this because I'm not sure it's really what you're looking for, but I really enjoyed it, so what the heck. It's called Rainbow Sleeves (http://archiveofourown.org/works/539042) by Lucy. It's StarkSpangledBanner with a female Bruce. She has some self-confidence issues and some trust issues to work through. It's also a WIP.
Here's the author's summary: Bryce Banner is on uncertain ground as she accepts a job with Stark Industries after the Chitauri Invasion. Her footing slips even more when she realizes that Tony and Steve seem to be offering her a place in their newly-forming relationship. Having everything she never knew she wanted is a heavy burden, and when General Ross teams up with an old friend in a plan to either capture Bryce or simply drain her head of all the knowledge of her creation of the Hulk, it feels almost welcome. At least she's used to fighting.
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Here's the author's summary: Bryce Banner is on uncertain ground as she accepts a job with Stark Industries after the Chitauri Invasion. Her footing slips even more when she realizes that Tony and Steve seem to be offering her a place in their newly-forming relationship. Having everything she never knew she wanted is a heavy burden, and when General Ross teams up with an old friend in a plan to either capture Bryce or simply drain her head of all the knowledge of her creation of the Hulk, it feels almost welcome. At least she's used to fighting.