The ultimate answer is that the shield does whatever the writer's (whether comic book or film writers) need it to do for the story, regardless of real world physics. It's a comic book item, after all.
As for in world explanation, I think the idea is just that Cap is just that smart and has practiced with it so much that he's able to pretty much instantaneously perceive and calculate how (at what angle, with the appropriate amount of strength) to throw the shield so that it's trajectory will have it ricochet off of objects (or people) in such a way that it will return back to him. I would think that he's probably one heck of a pool player.
There's also the fact that it's made from a fictional metal (that's completely vibration absorbent). Some have speculated that because of this, it's able to store the energy from the vibrations and when Steve throws it, some of this stored energy is used in how it behaves when thrown.
Nillindeiel
Agent Hill: ...Then aliens invaded New York and were beaten back, by among others, a giant green monster, a costumed hero from the 40's.... and a god.
Agent Ward: I don't think Thor is technically a god.
Hill: Well...you haven't been near his arms.
~Agents of SHIELD; Season 1 Episode 1 "Pilot"
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