There's a difference between software that's designed to be easy for people that haven't seen it before and software that's meant to be used by someone that's been trained to use it.
Yes and no. I did build several in-house enterprise applications and for this I know about this problem. And yes you're right, a lot of the complicated contexts are more complex than searching on Google.
But! Enterprise software architects have a tendency to make every feature as visible, and also making the apps as feature rich as possible. This comes with high costs.
I always try to establish a strive with exactly what google delivers.
Cage the user in his first decision, Filter or action and then show him or her the application with all the features feasible in the chosen context. It is amazing how complexity reduced most of these applications are when you just ask this first question.
I think it's more a case of needing to be idiot proof and provide the correct answer every time. Some people using it may have been trained but they also may be absolutely useless at using technology. Google may be simple but it doesn't give you exactly what you're looking for and all the relevant information on the first attempt.