Not entirely. The NEC is a set of rules intended to ensure public safety, but the problems an electrician is likely to encounter are not code related. Electricians must perform installations that meet the customer's expectations, can be done economically and are code compliant.
Most problems are technical or mechanical in nature, that's where experience comes in. It takes years of experience to solve installation problems, once you have chosen a solution, now you must use your knowledge of the NEC to make sure your solution is code compliant.
Good question.