I am going to guess that what you want to do is to fit a regression equation of the form NDVI=f(T-cap brightness) and then find R^2 for each function you try and choose the function that gives the largest R^2. First graph NDVI against T-cap brightness to get some idea of f. I assume the NDVI can be treated as continuous. Then get a copy of the book described in the link below. Full details for running your OLS regression can be found in Chapter 16. R^2 is part of the output. R is no cost, downloadable software. Instructions for doing that and getting started are in Chapters 1 and 2 of the book. The book is available as an ebook at the second link. as well. Best wishes.
Try to Google R for dummies. I think it is available free somewhere on the web. This book also covered ols regression in R, how to download the package and so on. Best wishes.