It can be plural when used with a noun which lacks singular forms or which refers to a collection of things, e.g.,
unae aedes; unae litterae. Also, when used with another number, e.g.,
similitudines, unae rerum, alterae verborum. Also, when used with the meaning 'single' or 'only', e.g.,
uni sex dies; tres uni passus.
It's worth reading Lewis and Short's entry for
unus:
http://athirdway.com/glossa/?s=unus