LabVIEW accepts as a command line option the name of a VI to open or a library and a VI to open. So if in the \temp directory you have a library called lib_test.llb in whict there are the first.vi and second.vi, you can create a shortcut to LabVIEW with the property
'labview.exe c:\temp\lib_test.llb\first.vi'
and LabVIEW will launched opening directly first.vi
Roberto