Excitation, orientation and alignment of a Na atomic beam is studied in a laser optical pumping experiment for the 32S1/2ff=2+-~32P3/2F=3 transition. For practical application in collision experiments with laser excited atom beams, we relate the observable parameters to several alternative descriptions by multipole moments, and discuss the experimental geometries most suitable for their determination. The dependences on laser power, atom beam density, small magnetic fields and spatial profiles are measured. They can be understood by simple rate equation models.