Yes.
Personally, I would never match a patterned or semi solid shirt and pocket square. But I personally don't see anything wrong with matching a full solid shirt and pocket square.
Funny. Personally I wouldn't come to that conclusion. I am not a big fan of either white shirts or white PS except for perhaps black tie or a very conservative charcoal or navy suit - just a bit bland even though it's a safe match. It does take a bit of work to get a good match between the shirt, tie, PS, and suit jacket. But when done well, the results can be quite elegant - and more pleasing to the eye than white.
But silk just drapes so much more nicely than linen.
If you're set on puffing them, then silk is better than linen. But I don't like white puffed silk if it's not for black tie. And generally, puffed silks work better in colours and patterns. If you want the flamboyant look of a puffed pocket square, then flamboyant colours and patterns would match. With a suit or sports coat, I'd say folded white linen is best. You can fold and press linen handkerchiefs in a variety of different ways.
I do the TV fold (where silk still drapes better than linen). At least in my experience. Even though my silk pocket squares are not flashy, they still look less dull than linen.
Why should drape matter for a TV fold? Nothing is draping with a folded pocket square. Linen is better than the typical silk pocket square (a satin-weave) for a TV fold because it can be pressed very crisp. A silk poplin or crepe de chine could be pressed, but typical silk pocket squares are satin.
This is odd. IMO with TV fold, the complete opposite holds true.
