Definitely in order of publishing.
If you go for the short route, start with the three original Foundation novels. If you want the touristic route and have enough time available, start with the first two Elijah Baley stories (The caves of Steel and The Naked Sun), then a few robot stories (I, Robot and/or Robot Dreams). Or, the other way around. Then, the later Baley-stories (The robots of Dawn and Robots and Empire). Then, Foundation, Foundation and Empire and Second Foundation. Finally, the last four Foundation novels: Foundation's Edge, Foundation and Earth, Prelude to Foundation and Forward the Foundation. Forget about the Extended Foundation novels, written by other people. Even though they're good books in their own right, they turn the Asimov heritage into an action fest that (gasp!) even could be used for a film script. Asimov isn't about action, it's about brains, and how violence is the last refuge of the incompetent.
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There is a theory which states that if ever anyone discovers exactly what the universe is for it will instantly disappear and be replaced by something even more inexplicable.
There is another theory which states that this has already happened.