I do not know the answer to your method export dwell time question, but hopefully someone else on the support board does.
When Skyline is detecting peaks in a chromatogram, the first thing that Skyline does is find the highest intensity along the entire chromatogram. Then, Skyline figures out the full-width-at-half-max from that maximal point. The next step of peak finding is to calculate the second derivate of each point along the chromatogram. However, since a chromatogram is a discrete set of points, and not a continuous function, the "second derivative" is actually a sort of weighted average of a rolling window of points along the chromatogram. The width of that rolling window is controlled by the width of that largest peak that Skyline found. This width calculation happens separately for each transition's chromatogram.
Another way to say this is that the width of the tallest peak on the chromatogram controls the amount of smoothing that happens when Skyline is looking for all of the other peaks along the chromatogram.
I cannot tell from your screenshot whether we are looking at the tallest peak along the chromatogram, or whether the tallest peak is on the part of the chromatogram which beyond the edges of the graph.
If you send us your Skyline document I could tell you more about why Skyline is doing what it is doing.
In Skyline you can use the menu item:
File > Share
to create a .zip file containing your Skyline document and supporting files including extracted chromatograms.
If that .zip file is less than 50MB you can attach it to this support request.
Otherwise, you can upload it here:
Another thing that can give you a little more insight into why Skyline is doing what it is doing is to right-click on the chromatogram and choose "Transform > Second Derivative". The only important parts of the second derivative view are the places where the curve crosses the X-axis. Those are the inflection points of the original curve, and are the places where Skyline starts from when determining peak boundaries. But, the exact way that the second derivative was calculated depends on the width of the tallest peak along the chromatogram.
Sometimes it is possible to change the peak widths of that Skyline ends up looking for by changing the Retention Time Filtering at "Settings > Transition Settings > Full Scan" so that Skyline extracts full length chromatograms. In that way, the tallest peak along the chromatogram might end up being something different.
I am not sure whether any of this information will be helpful.
I think the answer that usually works better is something about improving spray stability or chromatography.