Here's the technique I use for extra smooth paint finishes. You can get it almost to a glass like finish.
It works, but I sort of made it up for myself (ie. no research), so there are probably better ways of doing it:
1. Prime it. I like Kilz. You can get it tinted to help with the coverage.
2. Sand it very smooth.
- This is probably the most important stage to get right. If you don't get all the brush strokes out now, they'll be a pain (and almost impossible) to work out later. You may have to sand and prime more than once.
- If you have trouble getting the primer on smooth with a brush because of the brush marks, try a fine roller or a spray primer.
3. Spray on a glossy coat of paint. I've only done this with canned spray paint, but a sprayer might be best due to how many coats it typically takes. A roller might work as well.
4. Sand it smooth. Start with 220 grit and go up to 400 grit.
5. Repeat several more times.
6. This is the polishing phase, if you want it glossy keep going. If you're happy with your finish now, stop. Once things start looking uniformly smooth and the color is holding up, try sanding all the way up to 600 grit wet/dry paper. I'll even use a little water (emphasis on little). How high a grit you go depends on the finish you want. You may need to put another coat on still.
7. Polish it if you want it glossy (don't if semi-glossy is your thing). I've used a cotton cloth with Turtle Wax before with some great results.
It takes a lot of work, but really looks fantastic when you're done.