Do you have WSS or MOSS? The simplest way is to download a Word template of a Purchase Order, associate it with a document library and then use either a custom workflow (built with SharePoint Designer) or an out-of-the-box approval workflow if you have MOSS.
User will then do New - Purchase Order and the template will get loaded; user fills the document and save it. Various options are availalble to start the workflow (e.g., automatic start when a new item is created in the library, manual start, etc.)