Vinyl, like a lot of materials, will start out smooth but eventually develop porosity and gets rough. Have you ever seen a pool cleaner with rubber parts that have been submerged for a while? They degrade and get very rough.
That roughened surface texture is enough to pick up fine dirt and trap particulates. It's also a perfect place for metals to scale out of solution onto.
So yes, an old rough liner will definitely stain more easily than a new one.