As CoryPad pointed out, the principle stresses are the three mutually orthogonal stresses acting on planes which bear no shear stresses. For every possible state of stress, the principle stresses and planes are unique. They are directional with magnitude. If a crack is present, the max principle stress will be in the driver's seat.
Von Mises stress is a function of the stress state. Each state has only one value of the Von Mises stress. In continuum mechanics, you learn that any stress state can be broken down into the hydrostatic and deviatoric stress tensors. The hydrostatic stress is the stress which is trying to change the volume of an element of material. The deviatoric stress is trying to change the shape. The Von Mises is related to the deviatoric stress. The Von Mises theory of failure claims that failure of ductile materials is due to the change in shape (twist, pull, bending.)
Von Mises can not be used for predicting fatigue. (See Socie, Multiaxial Fatigue, page 418)
Just my few cents.
Doug