With version 4 (variant 1) random UUIDs there are 2^122 possible values. If we assume proper random* number generation that means that the chance of any two ids matching is around 1 in 5.32x10^36.
If you use 2 version 4 UUIDs together (let's call it a super UUID), you have 2^244 possible different values. That means the chance of 2 properly random* 'super UUIDs' the chance they collide is 1 in 2.83×10^73
So yes, having more numbers available makes it less likely but it was already incredibly unlikely in the first place. It's kind of like asking whether if you dip a cup in the ocean twice, a year separated, whether it's less likely to get the exact same set of water molecules on each attempt than you would if you did the same thing in Lake Superior.
*Unless you have special equipment to generate random numbers, then in practical terms we are really talking about psuedo-random numbers. As long as the PRNG is cryptographically secure (evenly distributed and chaotic, etc.) we can ingore that and treat them like true random numbers for this purpose.