Trespasser doesn't even unlock until you finish the main story, but it does prevent you from finishing any unfinished side content once you start it. It is, however, very upfront about warning you of this when you attempt to start it.
As for the rest of DLC, the other two main DLCs ("The Descent" and "Jaws of Hakkon") both have a fairly high level requirement if I recall correctly, somewhere in the 20s. These aren't things you're going to want to do early in the game. You can really do them anytime after you've reached the level requirement, before or after the story, but it will be late game.
The Descent is more of a singular experience, meaning it's something you'll want to do all at once. Jaws of Hakkon is structured more like other side content in the game. It adds a new region similar in size and scope to the other regions in the game, though it does have a more involved and engaging main questline than the quests you'll find in the other regions.
All of the other GOTY edition content is simply weapon packs and the like. The only true DLCs are these three, each of which is substantial in terms of the amount of content and time investment (Between 6 and 10 hours apiece). Any other DLC stuff on the map other than Jaws of Hakkon and The Descent you can feel free to activate whenever, they're just going to be giving you things like weapons and mounts.
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