I read the first two collected volumes of the New Avengers (post-Avengers Disassembled) and thought they were excellent compilations with strong storytelling. I was especially happy to see Spider-Woman, who I had never read before, take a leading role. I stopped after volume 2 in order to read the Civil War crossover event and related tie-ins. As a result, a little more than half of this collection is duplicate material also found in Civil War: Avengers.
People who are only reading the New Avengers, and not the events, may have a bit of difficulty following the first half of the book. The editors include more than one recap page to try and orient readers, but it's not the complete picture. However, if you've at least read the main Civil War event and preferably Disassembled as well, the story flows just fine. The book opens with the Illuminati one-shot wherein Stark intuits how passage of the Registration Act will come about. Thereafter, the book jumps from one Avenger to another showing how they respond to the law, until we get to the Confession. There's a lot of action and some heartrending scenes throughout. As I said, all of this material is also found in the tie-in. The benefit to also reading this book is seeing the action through the lens of the team. The first two volumes have the team dealing with the massive escape from The Raft supervillain prison and discovering something is deeply wrong with SHIELD and Hydra. Civil War shifts the focus from the "bigger picture" and this volume pulls it back in.
After The Confession, the book had new material I hadn't read before. Much of it will obviously lead into the next crossover event, Secret Invasion. The first story concerns Hawkeye, who was killed by The Scarlet Witch in Disassembled, then brought back in this new reality - fully aware of what happened. He goes on the hunt for Wanda. Meanwhile, Luke Cage realizes that something larger is at work with not only SHIELD and Hydra, but also the prison escape and even Registration. Stark has supposedly won the Civil War, with Captain America's surrender, but this small group of rebels refuses to give in. In Volume 2, the New Avengers traveled to Japan after the Silver Samurai. A mysterious hero called Ronin went along in Daredevil's place, and then disappears. Here, we learn who Ronin is when the hero calls on Matt and the Avengers for help escaping The Hand. The battle with the Hand overlaps with a confrontation with Stark and his hero squad. The action is fast-paced and incredibly exciting as Dr. Strange finally gets directly involved. And the battle with The Hand has a shocking conclusion.
Overall, despite much of this being duplicate material, I found this to be an excellent collection. The Hawkeye storyline was particularly moving and the battles at the end kept me on the edge of my seat while reading. Highly recommended!