One route would be;
Modular CPL/IR, along the lines of
PPL, hourbuilding/ATPL theory, night rating, ME CPL, ME IR.
Then instruct or paradrop to get the 700 hours required for single pilot CAT captain.
Then a chieftain/cessna 310/p68 job flying cargo, survey, charter, organs etc before moving up to king air, jet and so on.
The route still exists but is a lot less common than it used to be.
Sim hours don't count for the PPL for very good reasons!