How does a postal order work?

Walk into the post office and purchase the postal order (a fee is charged for it).

You will be provided with a postal order on which you can state the post office to be paid at and the recipient's name.
Post it to the recipient. They can bring it to their post office and get the value

For €10 probably cheaper to do a bank transfer if you can't do Revolut.
 
It;s just another antiquated paper payment tool. When the receipient gets it, they lodge it to their bank account and the bank treats it like a cheque and give cleared funds once An Post pay them