Mysterio or Octavious would make for good first villains in a new franchise. Most of the others work best with some set up. Scorpion should be created in the second film, and be responsible for Captain Stacy's death, setting up Jameson for blackmail. I'd save Kingpin for after Gwen's death, and have him be the villain that brings Peter back into action. Morbious' first appearance would make for a good movie, but with the black suit swapped out for the whole 6-arms gimmick. Hobgoblin and Carnage both obviously need Venom and Norman to come first.
As much as I love them, Shocker and Vulture both really only work as minor threats or henchmen, in my opinion.