I know this is a bit late, but this post is currently one of the top search hits related to finding alternatives in Debian.
The problem with using update-alternatives here is that it will only show you installed options as far as I can tell (its man page is pretty sparse).
To answer the question as posed in the title, i.e. finding all available packages that provide an alternative (whether installed or not), you can use:
aptitude search '?provides(pattern)'
which can also be abbreviated to:
aptitude search '~Ppattern'
where pattern is all or part of the alternative you are looking for. In the specific case of vi, this doesn't really work. If you inspect the packages nvi and vim with aptitude show or apt-cache show, you will see that neither one lists "vi" in its "Provides:" section. In fact, nvi's description is missing that section completely.
However, it works reasonably well for other alternatives, such as editor:
$ aptitude search '~Peditor'
p deutex - composition tool for doom-style WAD files
p edbrowse - /bin/ed-alike webbrowser written in C
p emacs24 - GNU Emacs editor (with GTK+ GUI support)
p emacs24-lucid - GNU Emacs editor (with Lucid GUI support)
p emacs24-nox - GNU Emacs editor (without GUI support)
p fte-console - Text editor for programmers - console edi
p fte-terminal - Text editor for programmers - version for
p fte-xwindow - Text editor for programmers - X Window Sy
p jed - editor for programmers (textmode version)
p jove - Jonathan's Own Version of Emacs - a compa
p jupp - user friendly full screen text editor
p le - Text editor with block and binary operati
p ledit - line editor for interactive programs
p levee - very small vi clone
p mg - microscopic GNU Emacs-style editor
p nano - small, friendly text editor inspired by P
p nano-tiny - small, friendly text editor inspired by P
p ne - easy-to-use and powerful text editor
p pluma - official text editor of the MATE desktop
p rlfe - Front-end using readline to "cook" input
p rlwrap - readline feature command line wrapper
p scite - Lightweight GTK-based Programming Editor
p vigor - nvi with the evil paperclip
p vile - VI Like Emacs - vi work-alike
p vim - Vi IMproved - enhanced vi editor
p vim-athena - Vi IMproved - enhanced vi editor - with A
p vim-gnome - Vi IMproved - enhanced vi editor - with G
i vim-gtk - Vi IMproved - enhanced vi editor - with G
p vim-nox - Vi IMproved - enhanced vi editor - with s
i vim-tiny - Vi IMproved - enhanced vi editor - compac
p xjed - editor for programmers (x11 version)
p xul-ext-password-editor - edit password manager entries in Mozilla
p xvile - VI Like Emacs - vi work-alike (X11)
Even though this isn't perfect, aptitude has incredibly flexible search capabilities that will often let you work around the problem of packages not correctly listing which alternatives they provide- for example using "~seditors ~dvi\s" as a search pattern will list all packages in the "editors" section whose description contains the string "vi ".
Another option is to uses Debian's packages website, where similar packages are listed in the section on the right.