Civil War is collected in a trade paperback, you can find it at Chapters or even Costco in the book aisle.
Marvel has a service Marvel Unlimited, $10 a month where on your tablet, computer or phone you can basically read every single comic they've ever printed in order like a comic Netflix. Civil War I, II, Infinity War, whatever. My 5 year old son and I read an Amazing Spider-Man issue in order every night, up to like #95 now. Would be basically impossible without this service, to find or even afford any of the early issues in real life. Started Daredevil from the beginning...
You can try out whoever and whatever. If it doesn't suit you, then whatever, move on. I've spent time reading everything from Iron Fist to New Avengers, Punisher from day one, Wolverine, X-Men, anything you're in the mood for. Cant recommend it enough.