Lightly spoon flour into a dry measuring cup; level with a knife. Combine first 5 ingredients in a large bowl; add 2/3 cup blueberries, and toss well. Combine buttermilk, butter, extracts, and egg; stir well with a whisk. Add to flour mixture, stirring just until flour mixture is moist.
Spoon batter into an 8-inch square baking pan coated with cooking spray, spreading evenly. Top with 1/3 cup blueberries.
Combine almonds, brown sugar, and cinnamon, and sprinkle over blueberries. Bake at 350° for 35 minutes or until a wooden pick inserted in center comes out clean.