I think the truth of the matter is that if your smart and some on here are not, you will find more experienced and useful CFIs than you will chief pilots. Why?
CPs for the type of organization you are considering starting with are usually guys who have been around a few years and either haven't had the ability to move on to bigger and better things or are just medium term seat warmers.
Very few (although there are exceptions) GA single engine charter organizations have "experienced" CPs.
The same is similar at flying schools, however there re plenty of high time CFIs who have returned to instructing after very interesting careers in all types of aviation. The CFI at every school I worked at and trained at were very experienced. One had a DFC from Vietnam, the other well into the 10,000 hrs, the likes on Ken Andrews, Trevor Howie the lsit goes on.
I don't recall any CP of start out organizations that has done more thatn a few scenics and indigenous charters out of some **** hole like Kunuurra. No comparison really.
There are exceptions to both these scenarios of course. If you intend making. A career out of either chose your employer carefully, you don't have o work for the first company that offers a job.