A plenary session is a session the whole audience attends at once, with nothing scheduled against it. Association and conference programs often use the term where others say keynote.
These overlap heavily. All three describe a session the full audience attends together. Plenary is the standard word in association, scientific and international programs. Keynote is the default in corporate and marketing events. General session is the common North American phrasing. Pick one per program and stay with it.
Plenaries exist to give everyone a shared reference point. They open and close programs, carry announcements that should not be heard secondhand, and host the speaker whose name sold tickets. Scheduling anything against one wastes the session you put opposite it.
A plenary needs a room that holds everyone, which is usually the most expensive space in the venue and the constraint that drives venue selection. It also compresses the rest of the day, because the whole audience moves at once, and five hundred people leaving one room need somewhere to go.
Sessions are created in the agenda with a type that determines how they behave, including a main stage format for sessions the whole audience joins. Capacity, access by ticket type and session registration are all set per session. See event agenda builder.