We don't know that was the first time they met since the war,
and Peggy's mental state was already in deterioration.
It wasn't the first time they'd met since the war, but the point of it was that, due to her deterioration, she was always slipping back into that first moment since the war. So even though they've surely had who knows how many conversations since he's been thawed out (and he's been thawed out for a year as of the events of The Winter Soldier), they still showed us what that first reunion was like when she realized that he was still alive. That's the heartbreak of that scene... because of her Alzheimer's and/or dementia, it's happening over and over and over and over and over again.
NillindeielAgent Hill: ...Then aliens invaded New York and were beaten back, by among others, a giant green monster, a costumed hero from the 40's.... and a god.
Agent Ward: I don't think Thor is technically a god.
Hill: Well...you haven't been near his arms.~Agents of SHIELD; Season 1 Episode 1 "Pilot"
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