I’m sure that in a very transit-oriented city like New York, car-sharing does generate some mode shifting from walking or biking or taking the train to driving, though I would guess that even in New York, the net effect of the service is less driving (in no small part because non-drivers are sure to find driving and parking in the city to be an extremely stressful and unpleasant experience). In cities where a carless lifestyle is somewhat more marginal (like Washington) the existence of a zipcar service is a huge comfort to those thinking about giving up their automobiles.
And I don’t think there is anything wrong with acknowledging the fact that for some things, the availability of an automobile is hugely advantageous. Carrying around big or bulky loads on foot is hard and unpleasant. The ability to use a car for, say, a trip to the hardware store or to the market in preparation for a big dinner party significantly increases the convenience of city life.
And that’s just as important as the effect of car-sharing on individual trips. Zipcar may mean that some trips which were previously taken on foot or by transit are now taken by automobile. But because using an automobile to ferry around huge items is so much more convenient than trying to do it on foot, the availability of car-sharing makes city life more attractive relative to the suburban alternative. And this should encourage more people to live in cities, which will indisputably be green, on net.
Now there may be other ways to arrive at the same level of convenience that don’t include driving (and given the fact that not everyone can drive, it may be worth exploring things like home delivery of purchased items and micro-mover services). But in general, I think car-sharing services are likely to be a clear positive for basically any city.