You want to get all of the printers to work no matter what applications print to them? You have how many PCs on your network?
In another post you state there are 20 printers configured.
So far, I do not know of any easy way to setup 5, 10, or 20 users to have the same settings for LibreOffice, and add over 10 printers in the mix makes it worse.
How many of these printers have a display panel build in? I know that you can set the default paper types there. But you still need to setup the LO application to default to the printer.
Is there any way you can setup a default
".config/libreoffice"
hidden folder and place it on every PC running LO. If you create one that has no user info in it, you should be able to copy it to the other Debian-based PCs. Windows users would be harder.
To be honest, I have only about 6 systems configured for, currently, three network printers. Two systems are dual-booting Ubuntu and Windows laptops.
But it seems you are wanting to set up many printers to the Postscript instead of PDF on several computers.
Sorry, but there is no easy way to do this.
As I said, you can use the LO Printer Administration application listed in the same menu as LibreOffice. That will be the easiest way to work on all of the printers that that computer has access to. Click on the printer and the Properties button. Go to the "Device" option and change the "printer language type" of the selected printer. That is the only way I know how to do it easily for all the printers that that computer has access to.
Then if you did not set up any information in the
Tools / Options / LibreOffice / User Data
that is only for that system, then you may have the "generic" ".config/libreoffice" information that could be copied to the other Debian-based computers you are using on your network. By replacing the original file with this "generic one" you should have all of the systems setup the same way. The only issue might be if you are running both 32-bit and 64-bit Debian-based systems on your network.
Of course I am assuming that you are not the only one on the network with 20 printers to do your bidding.