From a postal historical perspective, canceled stamps are more valuable. These have a very special charm: you can read a piece of (postal) history from them. The stamps reveal the place of use of the stamps, the date, sometimes the time and often many other circumstances of the stamp's use. We also learn that the stamp was used for what it was designed for: to postage mail.
However, it is directed monetary valuation of a collector's item always according to supply and demand. In a figurative sense, this means that the rarer and more sought-after a stamp is, the more valuable it is. If canceled stamps are rarer than unused ones, they are more valuable and therefore more expensive.
The rarity depends on various factors. Some stamps could only be used in a short period of time or in a small area. Therefore, these are rarely found stamped. Other stamps are rarely found unused because the unused remaining stock has been destroyed.
In addition, the preservation of the stamps plays a major role. Therefore, when determining the value of a stamp, you should always use a stamp catalog or even consult an inspector.