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I believe Advanced Sewing Kits are for repairing gear or can act as a support item when repairing (haven't used one myself but I have played a bit with repairing guns).
I think the armour you were has to be slightly damaged before you can use the kit.
As far as Toolbelt addons, what NPC and Rune have explained is correct. You will find Hide and even Ballistic Tiles/Patches that can allow small amounts of added protection when equipped to your belt, regardless of your main helm/armor.
Just be sure to look at the details of an item. If it has any radiation properties (or other ill-effects), this can hurt/kill you if you do not have something equipped to counter-balance it. Similiar to when using Artifacts. Ones that add radiation must be counterbalanced so the radition doesn't harm you.