I've thought long on this question. I think it's an interesting premise. There are 3 or so key factors IMO that give decisive advantages:
1: Plate Armor/Personal Armor.
The requirement was for defensive technologies and this is probably the closest to the request. Now, this would require for your alternate history that the Indigenous peoples discover smelting and Iron work - which is a pretty big technological leap, but they did have familiarity with Metalwork in general, mainly using Gold and other naturally occurring metals.
Why is this important? Plate armor gives the individual the single biggest advantage in Melee combat against crushing, stabbing and slashing weapons - against an unprotected opponents, it gives such a tactical advantage (until the significant advent of Firearms, which mitigates plate armor).
2: A 'Professional', well organized Army.
Enter Shaka Zulu! Bane of the British. I'm going to link to Wikipedia here - but the TL;DR - is that Shaka Zulu did the following things:
1: Issues standard equipment to his Troops
2: Regularly trained and drilled them
3: Had a focus on Logistics (amateurs study tactics, Professionals study logistics)
4: Discipline - Cowardice in battle was a death sentence for you and your entire family
Even with Spears and hide shields against Muskets and Cannon - The Zulus gave the British a damn good thrashing - they weren't ultimately victorious - but we still talk about them, we still study them and we still respect the hell out of them.
If we look at the Roman Empire (where arguably, the disparity in technology between the Romans and the germanic tribes was much much smaller) - the decisive factor was the organization of the Roman Army. An indigenous culture that has a bunch of Warriors, skilled though they may be, is no match for a well drilled and practiced army. As the Zulus have shown us, a well drilled army, with a significant technology disadvantage can still be victorious.
Granted, this isn't strictly a defensive technology per se, but I think it's something that you could and should weave into your story.
3: A Navy.
Most indigenous peoples had some form of Boat/River craft technology - obviously the closer the proximity to greater amounts of water, the more complex and advanced the Boat - look at the history of the Polynesian Peoples (Maori, Hawaiin, Samoan, Niue, Tongan etc. etc.) and how complex and skilled they were in Boat Building. In particular the Waka Taua (War Canoes)
But they didn't have a Navy. The easiest way to stop yourself from being colonized is to prevent them coming there in the first place - a successful Naval engagement (See Japan during it's isolation period) stops them setting foot on your land.
There were instances of the Maori successfully engaging the British/Dutch from their Waka and driving them off - but they didn't take the next step which is to formalize a Naval force. Each Hapu (sub-tribe of an Iwi - Tribe) would be responsible for their own Waka, it is consider a Taonga (Sacred/Treasure) - sometimes the Iwi would go on a War Party and multiple Hapu would join together with their Waka to raid another Iwi - but they never created a Navy whose sole purpose was the defence of the Sea and Rivers.