The officer who ran the programme that made Captain America, and who then spent decades building the agency the rest of these films work for.
Peggy Carter is the spine of the pre-Avengers half of this story. She is a British officer attached to the Strategic Scientific Reserve, she selects Steve Rogers for the serum programme, and after the war she does the part nobody made a film about for seventy years: she builds S.H.I.E.L.D. and runs it.
Hayley Atwell got a one-shot, then a series, then a place in almost every flashback the franchise needed, which is unusual for a character introduced as a love interest. Agent Carter is worth the detour: it is a 1946 spy show about a woman whose colleagues answer her phone for her.
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The reference article lists her across six films, the short film, two episodes of Agents of S.H.I.E.L.D. and her own series, and notes that she also appears in photographs in Captain America: Civil War. Photographs are not counted as appearances here.