AFAIK, in various comic book incarnations the serum gives Steve enhanced brain functions (not that he was stupid to begin with, even in the movies - do you remember the flag pole? Thinking fast and outside the box is kinda his thing), capability to understand new systems fast (I remember a moment from some story where he basically learns a new computer system in minutes), etc. So yes, he is smart and he learns fast.
But even if he has a normal thinking/reading speed of a normal smart person, the omportant part is that he is reading the Accords. He is not doing what some people were claiming he does - “just rejects them outright because he wants to decide everything himself or something”. And even with the document this thick, even some skimming can show the flaws, or, if you have at least some understanding of how military emergency services work (which Steve absolutely does), you just get the general gist of it and see where it all goes.
I haven’t seen this mentioned yet, but Steve actually knows how non-standard emergency teams work because that’s what the Howling Commandos were. They were what the Avengers are now, in a different situation and with less superpowers (except for awesomeness). The main difference is that there isn’t one large-scale conflict going on, there are many smaller ones but with larger killing power (probably) than WWII skirmishes. But the principle remains the same. And Steve can easily imagine what happens if you take all he’s seen in the interactions with the US military in WWII and put it on the global scale with 117 countries and people like the Rosses in charge. So he nopes from it very fast.
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