Any physical infrastructure, such as roads, is going to be distorted by local topography, which furthermore may not be entirely consistent from year to year (land can creep forward or hillsides erode somewhat). This deviation will tend to enormously outweigh the errors caused by map projection.
Another note is that legal boundaries tend to be defined on the basis of actual surveyed boundary markers, not on the logical definition of the line. So the US-Canada border, while originally defined as exactly 49°N, the actual border is actually generally about a few hundred feet south of that line. These surveys were generally conducted by people running literal chains in a constant bearing for some distance (maybe several hundred yards at most) and then taking another reading of their position to correct the line. Of note is the Mason-Dixon Line, which was precise enough to note that the errors in their surveying had a systematic error to them--which was realized to be the physical mass of the Appalachian Mountains ever-so-slightly deviating plumb lines from vertical.
Also note that historical boundaries were more often specified as "reference point and bearing" (or along line meridians/parallels, which amounts to the same thing) then "from point A to point B". In this regard, the straight line on a Mercator map is more accurate than the geodesic shortest-distance-between-two-points.