Msg#: 4309514 posted 8:21 pm on May 8, 2011 (gmt 0)
As SanDiegoFreelance says, you can either use Microdata or RDFa to do it.
Google do say that they can now automatically detect breadcrumb navigation (not marked up in RDFa or microdata) - and this might be true - but one of my sites does breadcrumb navigation like you mentioned in your OP and Google have never detected it. Then on a new website I marked it up with microdata and Google shown the changes in the SERPs within a week.
Msg#: 4309514 posted 5:20 pm on May 9, 2011 (gmt 0)
With regard to the character in use, on Google's Help page example, they are using › not > - that seems like an odd choice to me, because "greater than" makes at least some intuitive sense to me, compared to a "right single angle quote"