Do you:
1) Play the Peddler so that you can use the Scrying Pool on a "fresh" deck, increasing the chance that the spy effect combs chaff out of your way and hits a stream of action cards.
2) Play the Scrying Pool first so the friendly spy effect is guaranteed to actually discard a card that is bad. And the Peddler draws a "fresh" card later so this is really the better play.
If you don't want the Estate that is on top, play the Scrying Pool first. If you do want the Estate, play Peddler first.
Deadlock's simulation is correct that the number of action cards drawn is the same on average. So if you don't want the Estate, you draw more useful non-action cards on average by discarding it
I'm pretty sure this is correct. The decision is, do you want the Estate in hand vs a chance at drawing some alternative non-action card into hand later. (Keep in mind that having the estate in hand means it's not in your discard pile, so if you're going to shuffle soon, having it in hand could be pretty helpful.)
Here's how I think of it. The spy effect on Scrying Pool might as well read "look at the top card of your deck; if it's an action, draw it, otherwise discard it", since that's typically how it's played. That makes it a lot simpler to think about, because then the spy effect and dig effect don't interact.
If we make a big simplifying assumption that all your non-actions are junk and it doesn't matter whether they are in hand or in discard (which also means we're ignoring reshuffling during your turn), then the spy effect on Scrying Pool is effectively "draw a card". With this simplifying assumption, no matter which order you play pool and peddler, the pool's dig will be digging into an unknown part of your deck, so it's equally good. And it doesn't matter which order you play the draw effects in, so, therefore _with this assumption_, the order of play doesn't matter.
Now let's discard the assumption. The difference between spying a non-action with pool and drawing it with peddler is whether you put it into hand or discard. If you play peddler first, you guarantee the Estate goes into your hand. If you play pool first, you guarantee the estate goes to discard, then when you play peddler after, it has a chance of drawing a non-action, which would go to your hand.