Probably a combination of bank EFT or ACH transfer records, or credit or debit card charge records, identifying a merchant corresponding to the escort service. Or they subpoenaed the records of the escort service and he used his real name when booking. Fraudsters usually gain confidence over time, stop paying using large wads of cash, and switch to electronic payment. And this has been under investigation for over a year, thus, plenty of time to pull the records and build the case.
After leaving USPS, he was probably initially flagged by his banks detecting the structured deposits and reporting suspicious activity. They have pretty sophisticated algorithms to trap that. Or someone noticing his sudden luxury lifestyle.
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