Angle of attack (AOA) usually refers to the angle between the wing longitudinal axis (or effective chord line) and the air stream it is flying through.
Pitch attitude refers to the angle between the longitudinal aircraft axis and the Earth.
These can be widely different. For example, when a plane is diving it may have a -20° pitch attitude and a 0° AOA, a plane with quite a bit of power could be climbing at +20° pitch attitude and have a +5° AOA OR entering a loop with +90° pitch attitude and +10° AOA.
Wing sections stall at their respective critical AOA. Regardless of speed, pitch attitude or airspeed - right side up or upside down, a wing will stall at the critical AOA.
What makes AOA valuable is that it's a direct measure of "how close" a wing is to stalling. Airspeed is really an indirect measure of proximity to stall. The reason stall airspeed changes with configuration is pretty complex, but for various bank angles, density altitudes, loading, etc, the indicated stall airspeed will vary.
As for a plane stalling at a speed well above Vs, imagine a situation where the wing is forced into a high AOA condition. Whether by some "giant" grabs the tail and forces it down or the pilot's pulling back like heck, the wing may be forced beyond the critical AOA. Forcing the AOA to the critical angle like this will result in a stall - specifically, an accelerated stall (might break the plane too - be careful).
Back to the example of looping the plane, you have to be conscious of preventing the accelerated stall. Entering the loop or recovering on the backside, an unexpected accel stall can really wake you up or worse.
Hope his helps. anyone with a better explaination, jump right in.