I just read a piece on whether there could be a strong third party candidate in this cycle, and another about how Huntsman was interested in that. A third party bid is something that would keep Webb slightly longer than a doomed primary challenge.
Jim Webb's appeal is to the disaffecteds - those who are concerned about economic inequality and lack of mobility but also skeptical of big government and may be turned off by liberal identity politics.
There is also a type of primary voter who won't support someone who has been a national figure for 25 years. They're the people who went for McCain in 2000, Obama in 2008 and Ron Paul in 2012.
Webb could have a stronger appeal for that group.