Some site definition changes affect existing sites, others do not.
If you modify ONET.XML or any list definitions, those are recipes for
site creation, and therefore do not change existing sites. However,
if the site definition deploys files referenced from the file system,
like default.aspx, or master pages, these will update all existing
sites for which those files are not customized (unghosted). So if
you want your existing sites to be affected, you may need to reset
those pages to the site definition in SharePoint Designer.
It's generally better not to change OOTB site definitions. You can
copy them to a new definition and deploy to new sites. As for
existing sites, changes are usually better made as features that can
be stapled or just activated on existing sites, rather than updating
the existing definition.