A really good Steve centric fic is Captain Fraudulent by Ellidfics (http://archiveofourown.org/works/572602) A section of it talks about his life pre serum and being small and a starving artist. There is also a section called Captain Fraudulent The Outtakes which is really good.
NiennaNir (http://archiveofourown.org/users/NiennaNir/pseuds/NiennaNir) has a really good Avengers Series and two of hers are really good Steve centric:
Kodachrome (http://archiveofourown.org/works/911276) A storage container with Steve's name on it turns up in the bowels of SHIELD and its contents reveal startling truths about the past as well as the future he's living now.
Shock Factor (http://archiveofourown.org/works/957550) Super soldiers have amazing metabolism which is great for healing super fast. It's not so great if the super soldier needs anesthesia
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NiennaNir (http://archiveofourown.org/users/NiennaNir/pseuds/NiennaNir) has a really good Avengers Series and two of hers are really good Steve centric:
Kodachrome (http://archiveofourown.org/works/911276) A storage container with Steve's name on it turns up in the bowels of SHIELD and its contents reveal startling truths about the past as well as the future he's living now.
Shock Factor (http://archiveofourown.org/works/957550) Super soldiers have amazing metabolism which is great for healing super fast. It's not so great if the super soldier needs anesthesia