No you cannot force a file that is already committed in the repo to be removed just because it is added to the .gitignore
You have to git rm --cached
to remove the files that you don't want in the repo. ( --cached since you probably want to keep the local copy but remove from the repo. ) So if you want to remove all the exe's from your repo do
git rm --cached /\*.exe
(Note that the asterisk * is quoted from the shell - this lets git, and not the shell, expand the pathnames of files and subdirectories)