But to be clear, the mining fee on transferring 500BTC vs 5BTC is the same right?
The transaction fee is dependent on the size of the transaction
in bytes (after all, what you're paying for is storing data on the Bitcoin blockchain).
The size of the transaction in bytes can change depending on how you received that 5 BTC or 500 BTC that you're spending (how many
inputs the transaction has). It can also change if you intend to send the 5 BTC or 500 BTC to multiple recipients (having multiple
outputs).
In theory, you could send a 500 BTC transaction that cost less to send than a 5 BTC transaction, but you're more likely to have accepted a large number of payments in order to spend that 500 BTC, so the transaction is more likely to be larger.
It's certainly not percentage based, anyway.