Everyone needs to start with Dr No and Goldfinger. Then skip ahead to On Her Majesty's Secret Service. Check out some Roger Moore after that: a little Moonraker, Live and Let Die, The Man With The Golden Gun. I enjoy Living Daylights and License to Kill for what they are but I can't remember which is which. Then watch Goldeneye and Casino Royale.

(Feel free to watch more of the Brosnan ones as he is a great Bond, just be prepared for the utter ridiculousness that is the script and plot.)