... How many resistors would I have to buy to guarantee that a pair of them will perfectly (within 4 significant digits) match the value called for in the schematic? ...
This is a statistical question. The answer is an infinite number; the best you can do is improve the probability that a pair will match - no guarantee is possible.
You are asking for 0.01% accuracy. On average I think you have a 50% chance that one out of a hundred 1% resistors will match a given value to 0.01%, so there must be a 25% chance that two out of 200 will do so. Beyond that, I don't remember enough of my probability and statistics education to answer.
You can buy 0.1% resistors pretty readily, but only in selected values.