PurpleStarNova

Paint bucket? I've never used that.. You have to make the eye white shapes with the "Draw Bezier curves and straight lines" (Or using circles)

Then position it so the eyes are on the vectored face, then duplicate it (Using Ctrl+D) Select it then face, go to the "path" tab and select "difference", this will take the shape of the first one and cut it into the second shape..

From there, get the remaining eye whites shape and press Page Down a couple times to set the layering so it's behind the face shape.. Perhaps make them a little bigger so there's no transparent edges to the eyes.. You gotta do this so when you make the actual eyes (The iris and pupil parts) so that they sit in the actual eyeball and stuff and you can move them freely without them going outside the eye whites.. if that makes sense

here are the poses ^^