While the proportions of the cards start out the same (e.g., 1/13 of the cards are aces) things quickly go out of whack. Here’s a small example to illustrate what is going on:
Suppose you have both a single deck, and a 6D shoe. You’ve pulled a 10 out of each of them, and would now like an A to go with it. What are the chances?
SD: 4/51 = .07843
6D: 24/311 = .07717
As I said, that’s just a small illustration of part of what the difference is, but you can see that they are different, and that 6D is worse than SD for the player.