There is a different angle depending upon the angles of the moulding. Not all is even 45 degree (same amount covers the ceiling and wall), and the better looking/nicer stuff is something like 38/52 degrees, so the cuts and angles are different.
What ive found is that before starting the job, make a template set of each corner you might encounter, to help you set up your cuts faster and more definite. Pros have the intuition, but if you're a first timer like I was, it definitely helped. All my corners were perfect so I didn't need caulk, spackle, putty, etc. we had to be careful because mine was stained.
Many folks putting up moulding to be painted do a lousy job and just caulk or spackle their mistakes.