He needed a good financial adviser, so he chose Alexander Hamilton to be Secretary of the Treasury. The Secretary of the Treasury is concerned with financial and monetary matters. The most recent Secretary of the Treasury is Jack Lew.
George Washington knew he needed a strong figure to head the military. After the end of the Revolution, the army was by then a fraction of its former size, and the new nation's westward expansion was aggravating frontier conflicts with Indian tribes. Washington chose a military officer of the Continental Army named Henry Knox. The Secretary of War was responsible for all military affairs, including naval affairs. In 1947 the title was changed from Secretary of War to the Secretary of Defense (to indicate that the appointed official had dominion over the army, air force, and navy. The current Secretary of Defense is Chuck Hagel.