This sounds almost like a trick question: if you want to validate documents from the command line, you will want to acquire a schema validator for the schema language you have in mind with a command-line interface, no? So I guess you are asking which validators have a command-line interface?
Several XSD validators have command-line interfaces; in alphabetical order, the ones that come first to my mind are: MSV (multi-schema validator), Saxon-EE, Xerces C, and Xerces J. There are also partial XSD implementations in xmllint (the command-line interface to libxml) and xsv. I believe that it's also possible to run at least one of Microsoft's XSD implementations from the command line, but as you mention OS X in the heading I assume that's not where you want to go.
RelaxNG validators include Jing, xmllint, and msv; all have command-line interfaces.