1. The wait at immigration just depends on luck. I've waited nearly a hour at times. On the other hand last night after arriving on JL795 I went from plane to car, including picking up my checked bag, in about 15 min. If you are unlucky and another jumbo or two just happens to arrive at the same time it will take time. Anyway, there is nothing you can do about it. Plan between 30 to 45 min. and be thankful if it is less. Be sure to get the medical check card, entry card and customs card on the plane and fill them out before arrival.
2. Is it your first trip to Shanghai? If yes, then I would just spend your time here and not waste time on buses and trains. On the other hand if you have been to Shanghai many times before then I would agree that it would be a good experience to get out of the city.
3. There is a Citibank ATM machine just after you pass through immigration (and before you pick up your bags). In the city center there are many ATM machines, including Citibank ones in a few locations.
4. In general all shops in Shanghai are open 7 days a week.