Sentire is like "to hear". You can hear someone even without wanting to. Ascoltare, on the other hand, is like listening. You can hear people talking in the steet without even paying attention, but ascoltare is something you do on purpose, you listen to (ascoltare) someone who is talking to you.
The same goes for vedere and guardare. Vedere is like to see, you can see/vedere people without even trying to but guardare, just like to look/watch is something you do on purpose.
If you are talking on skype, for instance: can you hear me? = mi senti? (or riesci a sentirmi?) and can you see me? = mi vedi? (or riesci a vedermi?)