> you still have a higher chance of hitting something slightly off the middle than the perfect 100/100
That's because "something slightly off the middle" is a large group of possible results. Of course you can assemble a group of possible results that has a higher likelihood than a single result (even the most likely single result!). But you could make the same argument for any single result, including one of the results in your "slightly off the middle" group. Did you get 97 heads? Well you'd have a higher likelihood of getting between 98 and 103 heads. In fact, for any result you get, it would have been more likely to get some other result! :D
> But you could make the same argument for any single result
Isn't that the point? The odds of getting the "most likely result" are lower than the odds of getting not the most likely result. Therefore, getting exactly 100/100 heads and tails would be unlikely!