Like Don said, use enamels or lacquers. It's been ages since I've used enamels on a car body, but I've found Tamiya's rattlecan lacquers to be very user friendly. I've heard good things about the Testor's line of automotive lacquers, but haven't used them.
Also like Don said, practice. Find a couple of cheap kits and learn your technique on them.
YouTube can be your friend. Odds are there's a video out there on the model you're building, as well as tips videos. One of my favorites is The Scale Modeling Channel. He is strictly a car channel, but I like the way he does his videos.
Some tips on body prep:
Sand the body with some fine grit sandpaper (600-800 grit). It will remove the mold lines and help the paint adhere better. Wipe with rubbing alcohol to remove any sanding dust and skin oil from handling the model (or wear gloves, but still wipe it down for the dust).
Use a primer. I like Tamiya's Fine Gray. After it's dried, inspect the body for any dust particles that may have landed on the surface, as well as any mold lines you might have missed. If you find some, gently sand them down and reprime if necessary. Once you're happy with the way the body looks, go back and sand the body again with some fine grit sandpaper. You want a foundation that is as smooth as possible for the color coats. If you have a can of compressed air or a compressor handy, blow off the model and then wipe it down with alcohol again.
If the hood is separate, attach it to body with either tape from the underside, or simply glue it in place if you don't plan on showing off the engine. While not noticeable with most colors, if the hood doesn't get the same amount of paint, the color shift can be noticeable. That happened with my current build, I'm doing a white Mini Cooper and the hood was slightly darker because I didn't put an equivalent amount of paint on it. Will probably be a moot point as I may have to repaint the body because the black base I used for the chrome base bled through the masking in spots and the only way to fix it may be a repaint.
Applying the body color. Don't try to cover in one coat, especially if you didn't prime first. If you apply a coat of paint that covers in one coat on bare plastic, as it dries it will pull away from the edges of the doors, trunk, hood, etc. Since I tend to use a spray can to paint cars, I'll mist the first layers of paint on from about 12-18 inches away. This gives the paint some tooth and prevents it from pulling away from the panel edges. I wait about 15 minutes between coats. Depending on the size of the car, I find it takes about 4-6 mist coats before the body is covered. Your body will have a flat or matte sheen to it, that's okay. You're next coat will be a medium coat shot from about 12 inches away. Wait about 15 minutes, the shoot a wet coat from about 10 inches away. If you're satisfied with what you've got, set it aside and let it dry. If not, wait about 15 minutes, then apply another coat. The reason there is a wait time between coats is that it allows the paint to set, helping to prevent runs. This normally provides me with a nice, smooth, shiny surface that I'm happy with.
I wish I could say I developed this system, but I found it in an issue of Model Car Magazine about 15 years ago. The process doesn't stop there as he talked about rubbing the paint out to get the best shine possible, but that's another topic for another day. Hope this helps.