Spray Painting
Avoid heavy coats of paint
Multiple light coats will always give a better result than one or two thick, heavy coats. Build each layer up gradually - don't worry if the first few layers look patchy and uneven as it will soon fill in.
Start and finish each pass off the material
Point the nozzle just off to the side of the surface you are painting, and start painting. Move smoothly all the way across the surface, past the end of the area you are painting, and then release the nozzle. Move down slightly to achieve a satisfactory overlap and then continue.
Stopping and starting paint application pointed at the surface you are painting will give you runs and sags. If this will cause problems with overspray you need to mask off areas you don't want painting.
Overlap each pass slightly
As you are painting back and forth across your part you should overlap the previous pass slightly to build up an even coverage.
Don't spray too close
If you try to paint too close to the surface you will deposit too much paint in one location. If you are getting runs or orange peeling move a bit further away from the surface.
Don't spray too far away
Spraying too far away means the paint is too dry by the time it is reaching the surface. More paint will also be wasted as overspray, and it will take longer to apply enough coats to get a satisfactory finish.
Mask off anything you don't want painting
Overspray is a big issue with spray paint - if you don't want paint on a particular surface you need to mask it. Masking tape works fine for small areas, but you'll need to acquire in sheets of newspaper or similar to start covering up larger areas.
Overspray will also paint things you're not even intending on painting - like your phone or glasses - if they are in the wrong position. Watch out for other people's work hanging in the spray area, too.
Primer for excellent quality finishes, and weird materials
Not all paint will stick to all materials. Sometimes you need to have a primer paint in between which has good adhesion to particular surfaces. This is especially important when it comes to plastics and metals like Aluminium - always use a good quality primer.
Primer will also help improve the finish of your painting. Spray a few coats of primer, then sand it back with wet & dry sand paper to smooth out and lumps and bumps. Repeat a few times for the best results.
If you're covering a strong material - perhaps a very vibrant 3D printed material - you will find that primer will help cover over the bright colours and give the final finish paint the best opportunity. For 3D printing in particular a "high build" primer can help fill in and cover over layer lines.