I'm trying to determine if there is any flexibility in adjusting the Purchase Order form for the Vendor Center. I have tried to adjust the role on the form itself, and it seems the correct print-form comes through, but the UI is not great when they view the actual PO, and much unnecessary information is presented. I've tried to pull apart the URL to see if an adjustment can be made there. I've also tried a Before Record Load and Entry Workflow to set the custom form to another. Any other options available?

The Vendor Center is extremely limited, and many people build a Vendor Portal(custom portal integrated or within NetSuite) because of that.

Yeah that is the direction I have said, basically a type of scriptlet that gives a reorganized view of the information that matters.

To gain full control of your data presentation layer, you will need a heavily customized external Suitelet. This is not going to be a small project.

I think a window could be provided to the main level, with some custom data points added, but I'm no developer. We do have a dedicated DEV team at my company though thankfully.

There are a bunch of limitations and considerations, this will need deep understanding of NetSuite Suitelets and external Suitelets in combination with React or Vue or Handlebars etc... I wish I could tell you it would be as simple as a form with some data points, but it is not; you are going to be circumventing NetSuite imposed limitations by design.

Yeah this company has done that a lot haha, fortunately that aspect really isn't my specialty or concern haha.

suggested alternative would be Smartes Online Pages

I've seen this portal builder also be used for POs.