Calibrate your miter box by placing the saw in a pair of diagonal slots and measuring the angle the saw makes with the front wall with a protractor. If you're installing the trim in a wall with 90-degree corners, the angle should be 45 degrees. If it's more than 2 or 3 degrees off, cut a new pair of slots with the saw. Repeat the calibration with the pair of diagonal slots that face in the opposite direction.
Measure the length of trim you need with a tape measure and make a mark on the bottom edge of the piece you're going to cut with a thin pencil.
Hold a piece of trim in front of you in the orientation it would be if you if it were installed on the wall and you were standing in front of it. Now turn the trim around so that the edge that goes against the ceiling is facing the floor.
Set the trim in the box and arrange it so that the bottom edge is flush against the bottom of the box and the top edge is flush against the back wall. When you do this, trim will be angled exactly in the same way as it will be when it's installed.
Align the blade with the mark on the bottom edge. The blade can be angled in either direction, but when you cut the matching piece, you'll have to remember to angle the blade the other way.
Hold the trim securely against the bottom and back of the box while you make the cut.