Caster
This is the forward (negative) or backwards (positive) tilt of the spindle steering axis. It is what causes your steering to 'self-centre'. Correct caster is almost always positive. Look at a bicycle - the front forks have a quite obvious rearward tilt to the handlebars, and so are giving positive caster. The whole point of it is to give the car (or bike) a noticeable centre point of the steering - a point where it's obvious the car will be going in straight line.
Camber
Camber is the tilt of the top of a wheel inwards or outwards (negative or positive). Proper camber (along with toe and caster) make sure that the tyre tread surface is as flat as possible on the road surface. If your camber is out, you'll get tyre wear. Too much negative camber (wheels tilt inwards) causes tread and tyre wear on the inside edge of the tyre. Consequently, too much positive camber causes wear on the outside edge.
Negative camber is what counteracts the tendency of the inside wheel during a turn to lean out from the centre of the vehicle. 0 or Negative camber is almost always desired. Positive camber would create handling problems.
The technical reason for this is because when the tyres on the inside of the turn have negative camber, they will tend to go toward 0 camber, using the contact patch more efficiently during the turn. If the tyres had positive camber, during a turn, the inside wheels would tend to even more positive camber, compromising the efficiency of the contact patch because the tyre would effectively only be riding on its outer edge.
Toe in & out
'Toe' is the term given to the left-right alignment of the front wheels relative to each other. Toe-in is where the front edge of the wheels are closer together than the rear, and toe-out is the opposite. Toe-in counteracts the tendency for the wheels to toe-out under power, like hard acceleration or at motorway speeds (where toe-in disappears). Toe-out counteracts the tendency for the front wheels to toe-in when turning at motorway speeds. It's all a bit bizarre and contradictory, but it does make a difference. A typical symptom of too much toe-in will be excessive wear and feathering on the outer edges of the tyre tread section. Similarly, too much toe-out will cause the same feathering wear patterns on the inner edges of the tread pattern.
A reader of my site emailed me this which is a nice description of toe-in and toe-out.
As a front-wheel-drive car pulls itself forwards, the wheels will tend to pivot arount the king-pins, and thus towards the center of the car. To ensure they end up straight ahead, they should sit with a slight toe-out when at rest.
A rear-wheel-drive car pushes itself forward, and the front wheels are rotated by friction... thus they will tend to want to trail the king-pins, and therefor will want to splay apart. To ensure that they run parallel when rolling, they should be given some toe-in when at rest.
The perfect 4WD car will have neutral pressure on the front wheels, so have neither toe-in or toe-out... however very few companies make the perfect 4WD, so some will have a small amount to toe-in/out, depending on the dominant axle.
Your tyre wear pattern can tell you a lot about any problems you might be having with the wheel/tyre/suspension geometry setup. The first two signs to look for are over- and under-inflation. These are relatively easy to spot: