I think you would be able to see steam coming out of the cap.
Mine overheated for the first time a couple of days ago (albeit on a 150 mile trip) so I've been looking into this issue. The prime suspects are:
1 Expansion cap
2 Low level of coolant in the system
3 Poor ratio of coolant to water - should be circa 50:50
4 Air pockets in the system
5 System thermostat broken
6 Fan switch broken (is your fan coming on?)
7 Fan itself is broken
8 Dreaded headgasket
Perhaps you could tell us more about how it overheats, e.g. all the time, only at idle, is it drinking coolant, whats the oil temp like etc.