I apologize for such a simple question. It has been a while since I took math classes.
When you roll $2$ dice, there are $36$ possibilities. However, there are only $21$ combinations, if order does not matter. Rolling a $(4,2)$ = rolling a $(2,4)$.
Let's say in a game, rolling a $(1,1)$ makes you lose. The odds of rolling this is a $1/36$. But why can't you say the probability is a $1/21$, assuming you roll both dice at the same time? There's only one combination that makes you lose, so why can't you use $21$ as the denominator?
I have tried searching on this topic, but have not found a good answer. (Most likely because my thinking is fallacious.)

The key point is that if you distinguish the two dice all $36$ possibilities are equally likely. That is the only thing that allows you to convert number of possibilities to probability.
If you don't distinguish the two dice then there are only $21$ possibilities, but some of them are more likely than others -- and this issue gets more complicated the more dice you have. So knowing that there are $21$ possibilities doesn't give you a probability of $1/21$.
To extend your approach to a point where it more clearly doesn't work, suppose I change all the numbers other than $1$ to $2$s (so each die has $1,2,2,2,2,2$ on it). This clearly doesn't affect the probability of double-$1$, but now there are only three possibilities...