*for keyboard control manual, visit official site http://na.finalfantasyxiv.com/lodestone/playguide/win/manual/ *
A bit ago I learned to use the Pause (Break) button on my keyboard to make my character tilt her head to look directly at the camera (if anatomy allows). It is listed in the manual as “face camera” command. I think you can also assign specific key for it using Config => Shortcuts but I’m not in the game now so I can’t check.
It really makes difference for screenshots!
Camera is in good position and desired angle, but the character isn’t looking at the camera.
So if you hit the Pause button (next to Scroll Lock on my keyboard, and the Scroll Lock button is next to Print Screem/SysRq button) your character will face the camera.