Great question.
I’d start with the movie that (I think) is the most accessible movie to kids: The Spy Who Loved Me. It has a very simple plot, has some great BIG “Bond moments”, it doesn’t have many really “scary” moments (though Jaws may frighten them), and still has a little of the harsh edge we see in some of the best Bonds (Roger Moore is really channeling Connery’s take in a couple of scenes).
Then… well, things get tricky. I’d personally follow up with You Only Live Twice, but that might confuse the kids because a “different guy” is playing Bond. If you don’t want to do that, I’d show them with Moonraker.
Yep, the movie that many Bond fans hate, Moonraker. Again, it has some great big cinematic moments, it’s not too scary, and it’s Bond. In. SPAAACE! The kids should dig it.
Then… Well, I’d skip the rest of the Roger Moore films as well as the Dalton, Craig AND Brosnan films (I think all of them have moments that are inappropriate for kids). I’d jump straight to You Only Live Twice and then Thunderball, for the same reasons stated above.
Finally, I’d actually skip Goldfinger until they get older. It moves at a slower pace than the others and they may get bored. Yes, I know. SACRILEGE! But it’s true.