As you mentioned, there is no shortage of books on George Washington, and every year new ones are published. Many of the recent ones deal with a specific aspect of his life/his stewardship of the American Revolution/his Presidency/etc. Some of them are excellent, but they wouldn't give you as complete an analysis of His Excellency as some of the biographies. With that context, I'm going to recommend some of my favorite books about George Washington, both sweeping biographies and more narrowly focused books. I've read each of them, and own all but 1 or 2 of them. You did ask for 5 recommendations, but I'm going to provide more than that, and you can pick and choose from them to come up with 5. I'm listing them in random order; not preference or level of recommendation. Have fun!
1. First Entrepreneur: How George Washington Built His--and the Nation's--Prosperity, by Edward G. Lengel
2. Washington: A Life, by Ron Chernow
3. Washington: The Indispensable Man, by James Thomas Flexner
4. George Washington's Great Gamble: And the Sea Battle that Won the American Revolution, by James Nelson
5. The Indian World of George Washington: The First President, the First Americans, and the Birth of the Nation, by Colin G. Calloway
6. George Washington: The Political Rise of America's Founding Father, by David O. Stewart
7. Valiant Ambition: George Washington, Benedict Arnold, and the Fate of the American Revolution, by Nathaniel Philbrick
8. The Return of George Washington: 1783-1789, by Edward J. Larson
9. In the Hurricane's Eye: The Genius of George Washington and the Victory at Yorktown, by Nathaniel Philbrick
10. Cabal! The Plot Against General Washington, by Mark Edward Lender
11. A Crisis of Peace: George Washington, the Newburgh Conspiracy, and the Fate of the American Revolution, by David Head
12. Founding Father: Rediscovering George Washington, by Richard Brookhiser
13. His Excellency: George Washington, by Joseph Ellis