For instance, it's possible to mathematically prove in some cases that one algorithm is better than another; a set of ten nested for loops simply has greater time complexity than one. You don't need to actually test which algorithm is better.
And secondly, your intuition can be bad, but it's not guaranteed to be wrong, either. If you're a very experienced developer you might have a feeling about what's a more efficient way to code something up that could be in general, correct. Not every decision you make needs to be tested.
However, there is absolutely no point in arguing whose algorithm is better if there IS an argument about it since it can be tested easily. Also, if you personally are not sure which approach is better, test it.
And finally, you're actually in luck if you have two algorithms that you can test and find the better one. That's an easy situation to deal with. It's actually much harder if you only have one algorithm and it's a slow memory hog. Testing is only as good as the options you give it.
(On a related note, this is especially important to remember in science, too- testing hypotheses is only as good as the hypotheses you come up with to test. There could always be a correct hypothesis out there and you never even conceived of)