Hi gappy31600,
Your work experience no matter how long and inasmuch as it is not below 1year must occur within an occupation in demand in Canada. That being so, whether 5yrs or 10, the principle remains same, namely that you must apply to an occupation in demand and that has been identified by them as occupation demand list. That you must have a requisite work experience of atleast 1year duration in this profession. If you fail to meet these criteria, I'm afraid that you stand a greater chance of refusal should you decide to apply in an occupation not in demand.
That being said, it is pertinent to note that provincial nomination is aligned to CIC express entry program so that once nominated, nominees can accept it CIC and that will result to a boasting of ones point by additional 600! That being so, if you have a CIC profile and let's say you meet FSW criteria, you will be eligible. Then, this means that you are eligible for nomination as well. But if you try to create a CIC account with an occupation not in demand list, then, your guess is good as mine. At any rate, whether you have 10years experience in a not demand occupation, and have just on the dot 1yr in demand own, you must ensure that you meet all criteria for migration of which you are expected to apply in a demand occupation. Also, whether you have a PhD, MSc or Bachelors, you must provide an ECA to back it up except you had them in Canada. So do the right thing and all the best.