What width rims do yo have?
The matching pairs of concave/convex washers differ in thickness to allow for different rim widths so that the pad contacts the rim as close to parallel as possible.
Use whichever pair adjacent to the brake shoe that gives the best compromise.
http://www.koolstop.com/english/pdf/Inst_VBrakeThreadedthin.pdf
Sorry, I'm a novice at this so could you explain please what you mean by rim width? Which measurement are you referring to? How does one choose which washer combination to use with a particular rim width?
Refering to the Koolstop illustration that I linked to earlier.
http://www.koolstop.com/english/pdf/Inst_VBrakeThreadedthin.pdfThe rim width is the distance between the braking surfaces of the rim.
In the head on view you can see that the brake pads are set to contact the rim parallel to the braking surface. A substantially wider or narrower rim would see the brake shoe making contact with the rim at a slight angle. The brake shoes are supplied with matched pairs of convex/concave washers which when paired together are of differing overall thickness. One pair goes on either side of the brake arm. The thickness of the washer pair fitted immediately adjacent to the shoe governs the geometry of the set up. With the thicker pair fitted adjacent to the shoe it will space the shoe away from the arm and will generally suit a narrower rim. Similarly the narrower pair will better suit a wider rim.
In practice the exact geometry is dependant on a number of factors. Most notably the exact height and distance apart of the brake mounting bosses. Also, despite initial set up, the pads will wear increasingly unevenly as the brake shoes wear down, as in julio's illustration.
The other purpose of the convex/concave washers is to allow the brake shoe fixing bolt to swivel in relation to the brake arms. This allows for precise alignment and in particular the setting of toe-in, whereby the leading edge of the shoe contacts the rim ahead of the trailing edge.
For a good explanation of all of this, including the setting of Toe-in, see this park tools web site.
https://www.parktool.com/blog/repair-help/linear-pull-brake-service