the choice of MVC versus webforms have little/nothing to do with the ability for the app to handle load. Your problems will be reading/writing to the DB, and that doesn't change no matter which of the two you choose.
ideas for improving ability to handle load:
first and foremost: absolute minimum is two servers: web server and DB server, they should NEVER run on the same box.
DB:
Efficient queries towards the DB, indexes in the DB, denormalizing tables that are hit a lot, CACHE, CACHE CACHE, running the DB in a cluster, oh, and did I mention CACHING?
Processing:
if you need heavy processing, do this in web services that can run on separate machines from the web servers so that you can scale out (buy more servers and put them behind a load balancer if needed)
WEB:
avoid the need for server affinity (so that it doesn't matter which web server serves a given user at any given time) this means using DB or StateServer to store sessions, syncing the MachineKey on the servers.
the decision of using MVC or not have NO impact on the ability to handle 10k concurrent users, however it's a HUGE benefit to use MVC if you want the site to be unit-testable
remember: Applications are either testable or detestable, your choice