In short: if you want to be a Petroleum Operator it's better to join as one.
Transferring is an option and lots of soldiers transfer roles successfully, but it isn't a decision that should be taken lightly. To understand why, you should try to view it from an employers perspective: each position takes a lot of time, money, and effort to fill, and there won't always be somebody waiting to fill that gap if you leave. You'll also need to be interviewed and show a very high standard by the Corps taking you on to be able to transfer. If you're transferring within the same Corps it can be easier, and if you're moving from a role that is over-staffed to one that is under-staffed if can be easier again.
I hope that helps, feel welcome to ask any follow up questions in the comments.
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