Is that all he does is get a little startled when you open up the enclosure? Or does he also get startled if you try to hold him?
And some important questions:
Has he always behaved this way since you first got him?
Is he blind, either in one or both eyes? I know, it seems kind of foolish to ask since snakes don't depend much on their own eyes and rather detect by heat, but they do see out of their eyes - so if they are blind it only gives them more of a reason to be cautious if they are not able to see their surroundings very well. A blind snake could just hear something and not know what's happening so they get startled.
Did you get him from a breeder or from a pet store?
Can you contact who ever gave you the snake? If so, I suggest you do and ask if your pet has had behavioural problems like this when they had him and if so, ask what precautions they took. You're most-likely to get this information from a breeder though of course, since pet store people usually don't take enough care into the pets they have.
One suggestion that seems really obvious :
Have you tried being extra careful when opening the enclosure? I suggest that maybe you could bit by bit, try opening it very cautiously and slowly. Maybe even try to gather up all the patience you have and try opening it up little by little every minute or more and see how he reacts by that.
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