I think it is possible to do it in Excel by writing the correct formula, but it will be much quicker to use, for example, iGraph package in R. Please take a look to this page http://igraph.org/r/doc/assortativity.html
You can find there both - existed command for R and formula that You can program in Excel
Well, I never used Excel for this, but i think the simplest case can be solved like this (please see attachment). However, have to say that I checked the results in R and got close, but not exactly the same number. I guess R uses more correct formula, while here in excel I used a simple correl-function. Will be grateful for any corrections.