Electron orbitals are most stable when they are fully filled or half-filled. In the case of Chromium, and Copper after the 4s2,3d4 and 4s2,3d9 respectively configuration is attained, an electron from the 4s orbital jumps to 3d subshell because 3d5 and 3d10 is a much more stable configuration than 3d4 and 3d9. That's why chromium and copper exhibits such electronic configuration