Applications that works in fullscreen (mpv, vlc, video games) requires you to set them fullscreen/floating, either yourself with a keybinding (Mod+f on awesome) or through the wm's config file. Some applications do not like tiling at all, some java gui apps from what I remember, but there are so few of them that I can't actually give you any example.
I say give it a shot, but beware: controlling your desktop entirely from your keyboard is addictive.
(awesome 4.x is more mouse friendly than awesome 3.5: in addition to the above, you can also change a few client modes with the mouse: float/tiled, maximize, stick (ie. display on all workspaces), on-top, close.)
Keyboard only: adding/removing columns/masters, moving a client to the master area, resize master area, move client to another workspace/screen.