How accurate is the law of superposition?
The principle does not apply to all materials on earth as observed by us but is primarily concerned with sediments and rocks that form from sediments. Since sedimentation is a process driven by gravity grains settle one on top of others and there is no possibility to change that without adding additional processes. So from this perspective the principle is 100% in situations where it is applicable. 

It is of course not uncommon to find situations where older material overlays younger. In such cases there has been additional forces (natural mind you) in action. It is for example possible for intrusions (magma) to be injected in older solid rocks thus completely changing the age sequence. It is also possible for crustal movement (tectonics) to fold the bedrock and thrust parts of the bedrock to overlay other parts hence creating situations where younger rocks seem to undelie older. It is also possible for sediments to slide or move downslope so that a reverse or at least disturbed age sequence is established. I could continue ad infinitum. 

So many possibilities exist to obtain such cases but always with a logical explanation involving post-sedimentary processes. To correctly interprete observations, one has to have gained full understanding of the geological setting and history as well as physical processes. It is not generally wise to look at an outcrop or cut and create a larger scale interpretation without such background knowledge.