It has everything to do with rarity. Sometimes there are more unused stamps available than used, because it has only been available for use for a very small time, or it was used in a country in war or economic trouble (meaning that most people had something else to do than writing letters).
I'm thinking that to be considered at the higher value, the used stamp would have to have a clear cancel on it with a date sometime around when the stamp would have originally been used. Otherwise someone could get the unused stamps and put them through the mail now just to get a cancel and try to make them worth more.
Great question Tina, as Jan-Simon said, everything to do with rarity.
If you have a Scott's catalog, go to the semi-postal section for Switzerland, B- numbers, and take a look at the used values for semi postals issued in the 1940's and 50's.
Some of those used stamps, run up to 10x's the value of MNH
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