Since upgrading to OS X Mavericks, I can't open any files on a SMB share from my Windows 8.1 PC
This seems to be a known issue as I remember running across a work-around the other day at TUAW:

http://www.tuaw.com/2013/10/27/did-mavericks-kill-your-network-drive-access-heres-a-fix/

Basically what they are telling you to do is replace the SMB:// in the Go > Connect To Server... dialog box with CIFS://

I gather this forces the Mac to use an older version of the SMB networking standard that is the default on Mavericks. Not sure if this will work in VLC and not sure how to compensate for the issue on a PC but this should help when you are working on the Mac end of things...