Hopefully I can somehow ease you out of that intimidation. Most of the mythos of Valiant has been built from the ground up since the relaunch in 2012. There are some callbacks to the 90s stuff, but it's scant. The Valiant is a great story for jumping on because it provides context for a handful of heroes, and also gives you a glimpse at the larger universe. The kicker is that it's actually an event, yet it's one of the most self-contained and compelling tales I've read from Valiant so far.
From there, you can pretty much pick up any of the solo series without any prior reading if you end up liking it. Most of the series that they started in 2012 have already ended (most of them started with a planned 20-25 issue run), with the exception of X-O Manowar and that's probably the only one I would really recommend starting from the beginning. They launch fresh books every so often to provide readers new jumping-on points, like the recent Ivar, Ninjak, or Imperium ongoings.