The standard method for 2d10-as-1d100 is to designate ahead of time which die will serve as the tens digit and which die will serve as the ones digit, treating a roll of 00 as equal to 100.
From a probabilistic standpoint, this is equal to 1d100. The key to understanding this is that you don't add the numbers up: each number is its own digit, independent of the others. This is what makes it work. There are two factors at play in that:
- There are no outcomes on 2d10 which produce a result that couldn't be rolled on 1d100. Likewise, there are no result on a d100 that can't be produced on 2d10.
- For every result that could be rolled on 1d100, there is exactly one 2d10 outcome which produces that result.
Let's compare this to, say, a claim that rolling 2d10 and summing the numbers (treating a 0 on each die as 10) is equivalent to rolling 1d20. The dice involved in the two claims are the same, but your claim is equivalent and mine is not.
Your claim fits the first point: I could name any result that a d100 could roll, and show how 2d10 could roll it. I could also do this backwards: if I name any result that 2d10 could roll, I can show how 1d100 could roll it. My claim fails this test, because I can roll a 1 on 1d20, but I can't roll it on 2d10.
Your claim also fits the second point: for any number I named that 2d10 could roll, I can show only one way to roll it. The real key here is that each result has the exactly the same number of ways to roll it: that number happens to be one, but that doesn't really matter here (though it makes the math easier). Because of this, all numbers on 2d10 are equally likely, just like on 1d100.
My claim is different. There's only one way to roll a 2 on 2d10 (1+1), and there's also only one way to roll a 20 (0+0): these two numbers are equally likely. But, for example, there are three ways to roll a 4 (1+3, 3+1, 2+2). This means that a 4 is more likely to come up than a 2. That's not like 1d20, where all results are equally likely, so they're not equivalent.
This is why 2d10-as-digits is equivalent to 1d100, even though 2d10-and-sum isn't equivalent to 1d20.