One's a depressant and the other is a stimulant (a "downer" and an "upper" in ~ 60s era parlance ).
The problem is the caffeine counters some of the effects of the alcohol while you are still being increasingly intoxicated. This is why drinks like Four Loko were getting a lot of negative attention a few years ago, because a number of teens and college students were getting blackout drunk and landing in the hospital.
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