Largely speaking, yes.
First off, we need to clear something up: Captain America: Civil War doesn't exist quite like that in the comics. The Civil War storyline is a giant crossover event made up of one core comic series, with ancillary stories across multiple (and many) other books.
If you want to read the bare minimum storyline for Civil War, you must read the Civil War books. The story crossed over into Captain America's own book, but it is "extra" story.
The 90+ issues which make up the crossover event outside of the main Civil War book are within books like the Avengers, Wolverine, Spider-Man, Iron Man, Captain America, Black Panther, et alia.
By and large, the story is fairly self-contained. You can read it and get a general understanding of what's going on even if it's dealing with characters you're not familiar with (there were a few even I wasn't).
So you can, but should you?
Not really. While the main book is largely self-contained, the character development and explanations for their motivations are all in the crossover books. Reading only the main Civil War books is like reading the wikipedia entries.
Do you really need to read all 100+ books?
No, no you don't. Generally speaking, you can skip most of the titles of characters which don't seem interesting to you, but the Captain America, Spider-Man, and Iron-Man books are pretty essential to the main storyline and plot/character development.