When you press F5 in Chrome, it will always send requests to the server. These will be made with the Cache-Control:max-age=0 header. The server will usually respond with a 304 (Not Changed) status code.
When you press Ctrl+F5 or Shift+F5, the same requests are performed, but with the Cache-Control:no-cache header, thus forcing the server to send an uncached version, usually with a 200 (OK) status code.
If you want to make sure that you're utilizing the local browser cache, simply press Enter in the address bar.