For a tiered cake to serve 100, I use a 13” bottom, 10” middle and 7” top; the entire cake is served (no saving the top tier). Depending on who is doing the cutting, you may end up with a few more servings, but better to have enough than not.
I use the chart found online at http://www.earlenescakes.com - she has a useful chart online that can help.
With two or three different methods of cutting a tiered cake, I’ve found it’s better to use a generous serving size. If there are other desserts being served, or if the cake is served as a dessert station (people help themselves to the cake slices nicely arranged on a platter) you won’t need a serving for each guest. But if the cake is plated and served at the table, you do. No one will ever complain about having some extra cake; but you would never hear the end of it if you ran out. When I first started out, I had an order for a wedding cake for 100. When I arrived at the site, I saw that there were 15 tables set; there were 150 guests. I asked the coordinator how the cake was being served, and she said plated - and I told her that the client had ordered only 100 servings. At least she knew ahead of time and could plan for it, instead of realizing half way through cutting it that there wasn’t enough. A year later, the sister of this bride came to me for her wedding cake, and told me how the slices were so thin you could read a newspaper through them; they were able to plate and serve all the guests, but it wasn’t a true slice of cake! So I learned to always ask how many guests and how the cake is to be served so I can suggest options for sizing to the client.