This would likely show Natasha during her early years in the US after the fall of the Soviet Union, when she first gets involved with S.H.I.E.L.D. Since Hawkeye and Natasha work together for years before the Avengers forms, it's safe to assume that he will be in the movie as well. But then again, we also assumed he would be in "Infinity War."
Winter Soldier's involvement could be quite significant. In "Captain America: Winter Soldier," Natasha mentions a run-in with him, and it probably wasn't just throwaway dialogue:
"Five years ago I was escorting a nuclear engineer out of Iran, somebody shot at my tires near Odessa. We lost control, went straight over a cliff, I pulled us out, but the Winter Soldier was there. I was covering my engineer, so he shot him straight through me. A Soviet slug, no rifling. Bye-bye bikinis."