'Slumped over' is an adjective that describes a certain position. This position is one where the person is in a sitting or semi-sitting position, and the upper body is leaned forward over something, such as a desk or table. It is usually used in situations where the person gets into this position involuntarily, such as dying, losing consciousness, after a seizure, etc.
'Hunch' is a verb describing the lifting up of the shoulders (not the arms, just the tips of the shoulders) and arching the upper back forward. Picture someone who's trying to avoid security cameras that are perched above. He would walk with his face down, and with his shoulders rounded upward (so as to further hide his face). Another example, picture the Hunchback of Notre Dame.