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It could be that it's always been that way or perhaps when the house settled, it just settled a little bit more on that end. Or it could be a structural problem that an inspector would be able to see right away if there's any separating happening where the ceiling and wall meet or where the wall and floor meet, or if there any major cracks around doors and windows. He'll look not only at that second floor, but also in the attic space above at the joists and rafters and the roof, on the first floor beneath as well as whatever is under the house on that side (basement or crawl space) and the foundation.
It may be that when the addition was put on, the ground was disturbed enough to affect the settling of the house on that side although I would think the first floor would have been affected, too, which it appears it wasn't.
Is the addition attached to the main house directly below that second floor room? If so, and presuming the addition's roof is attached to the main house at the second story floor level, its weight and settling may have initially "pulled down" on that part of the main house. Again, an inspector can look at the structural elements of the addition and see if there are any issues.
As a layman, you can visually inspect these areas yourself, looking for glaring problems such as warping or cracks or separations. These things are quite evident to an untrained eye even if previous owners have tried to mask or repair them. I wouldn't rely solely on a self-inspection, but if no red flags go up for you, chances are that the angled floor is just an "oddity" of that house and won't be a problem.
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