When your husband says that you hurt him, he is looking for you to acknowledge how he feels. When you go on the defensive to protect yourself and list how he has hurt you, you are invalidating what he is feeling at that moment. It also shows that you are thinking only about yourself and not caring about him, so he is further hurt by your reaction.
Defensiveness never accomplishes what it sets out to do, which is to show that you are innocent of damaging his feelings. He is hurt, and whether you agree with why he is hurt or not, the fact remains that it is something that you said or did that gave him the pain. It is a self centered reaction that causes your husband to feel that you have little compassion. And, honestly, he's right. If your primary concern was for him and to repair what caused the hurt, you would not be defensive. You would reach out to him with empathy and love and apologize for what you did. When you defend yourself and refuse to apologize, he is hurt doubly, and if you continue in your defenses, it just gets worse and worse.
My ex husband was defensive like you. I cannot tell you how much it hurt me when he would refuse to acknowledge my feelings to protect his pride. It damaged our relationship horribly, and is one of the primary reasons that he is my ex. Thankfully, my current husband and I always acknowledge each other immediately, even if we don't agree. Either one of us can say "that really hurt me", and the other will immediately move to heal that wound. Then we go on to have thoughtful, considerate conversation about what bothered us. The reason we do this is because our love for each other is far more important than any disagreement we can have. Knowing this, we are both able to check our negative emotions and seek to be loving and kind towards each other.
You are absolutely capable of stopping your defenses when they bubble up. In the heat of the moment, check yourself and think about him instead of yourself. If the defensive words start, stop yourself immediately and say something like "I'm sorry, I'm reacting selfishly. I'm sorry I hurt you. I love you and I don't want to cause you this pain. I understand why you feel this way." Then discuss what happened and tell him what you will do to avoid it in the future.
Hurting our spouses is inevitable. Sometimes it happens for reasons we don't understand, because we push buttons in our spouses that run deep. The important issue is that in that moment he is hurting, rightly or wrongly because of you, and as a loving spouse, it is up to you to prioritize his feelings over your own desire to be combative and accusatory. He needs to do the same for you. If you do, in the long run your relationship will improve because you can tell each other when you're hurting without fear of a fight, and talk thinks through calmly and with maturity.