I believe that it is erroneous to believe that this has anything to do with software. Estimates in most or all fields are off because humans are bad at predicting timelines. This is referred to as the planning fallacy: http://en.wikipedia.org/wiki/Planning_fallacy
I heartily recommend reading the studies associated with the Wikipedia page, as they demonstrate that this applies to more fields than just software. I will agree that the data does appear to support the hypothesis that the less repetitive the task, the more likely it is to fall subject to the planning fallacy.