I honestly think all Steve knew is what we, the audience, were in fact shown.
Zola shows clippings of the Starks' deaths followed immediately by a photo of Bucky as TWS
The implication is that Bucky killed them.
But we (and Steve) don't have confirmation of that, even after the HYDRA files were released. That's why Zemo needed to find someone (who turned out to be Bucky himself) to give him the "mission report" from December 16, 1991.
I believe Steve was being honest when he told Tony, "I didn't know it was him [Bucky]." Steve only said, "yes," to Tony''s next question ("don't shit me Rogers, DID YOU KNOW?") because he knew, at that moment, Tony wouldn't accept any other response.
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