Isn't it self-explanatory?
A 3-way switch has three positions. On a two-
humbucker guitar, that means you have three pickup selections:
- bridge
bridge and neck together
neck
Depending on the kind of switch, sometimes you can do different things with the switching options at each position, such as splitting two humbuckers in the middle position.
A 5-way switch has five switch positions and was first introduced because Strat players wanted to get those "in between" combinations on a three-pickup guitar. Typical 5-way switching (with three pickups) goes:
- bridge
bridge+middle
middle
middle+neck
neck
Of course, with modern pickups and newer "superswitch" type 5-way switches, the possibilities are almost endless in terms of the exact coil combinations you have access to in each position.