Read here a detailed tutorial on how to print Purchase Requisition in SAP. In short, the PR cannot be printed in SAP as SAP doesn't give Output determination for a PR document. It considers purchase requisition as internal document which are not relevant for external communication. The only way to do this is to write a custom program and trigger the print.
There are a few print buttons in ME53N and ME53A, but those are merely to print the list and not to generate a smart form.
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