Rainford-Brent played 22 ODIs for England as well as seven T20Is...
Stokes will cover regular captain Joe Root, who misses the first Test as he attends the birth of his second child.
Holder has led the West Indies for nearly five years.
Last month, Vikram Solanki took the reins at Surrey to become the only head coach among the 18 first-class counties from a diverse background.
A game-wide anti-discrimination charter and code will be introduced.
Stokes will be skipper for the first Test against the West Indies, and Root took the time to write a short note to his stand-in.
A majority vote was reached at a meeting of first-class counties chairmen on Tuesday.
The Durham man tiptoed around ICC rules on overt political statements but made clear the occasion would not go unmarked by England.
Contests between the two sides have seen a number of record-breaking performances.
The former England spinner insists Test cricket can survive a summer without crowds.