This may be a moot point, since this thread is so old, but all the explanations here don't quite get it right.
Winston was definitely going to kill Jerry, and probably Samantha, too. When he saw the Mexican in the glove compartment, he knew that he didn't need either of them alive anymore. In fact, he needs them dead because so they can't rat him out to Margolies. When Jerry is changing the tire, Winston pulls the gun on him and is about to pull the trigger (which Jerry sees in the hubcap), but then he sees all the traffic coming, and he drops the gun to his side, out of sight of the oncoming traffic. He then volunteers to change the tire, most likely with the idea that he should probably kill them in a more secluded area.
Now that Jerry knows that Winston is going to kill them, he pulls his gun on Winston while Winston is changing the tire. But then he looks up and sees Samantha, and he knows that he can't do it - if he shoots Winston in the back, it means that he's no different from Winston. If he does that, there's no way he'll ever get Samantha back. In that moment of hesitation, you can see him waver, and he lowers the gun a little bit; Winston catches that in the hubcap, and he seizes the moment to turn and pull his gun on Jerry. Jerry shoots Winston in that moment not in cold blood or malice, but in self-defense.
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