You've hit on what I think the core problem is: since forever (as far as I know) computers have been regarded as "magical and incomprehensible" - that is, non-technical people think they will never be able to understand what you just did with the proxy settings. So even if you show them and explain what you did, they never even consider that they could use that knowledge again in the future.
I think this is a failure of education. As the author points out, learning MS Office shouldn't be the first step, learning the principles of technical problem solving should be. That most computers operate the same way regardless of what they look like, and that you can draw inferences about what's wrong, and where to make changes. It seems like drilling in 'try a few things and then google for it' (as we all do) would help a lot.
Certainly unwillingness to teach can be a problem, but I think often it's born from the experience of solving the same problem for the same person many times over, and seeing their unwillingness to learn. </huge_generalization>