I decided to post this answer which does use a regular expression.
^(?:[a-zA-Z]\:|\\\\[\w\.]+\\[\w.$]+)\\(?:[\w]+\\)*\w([\w.])+$
Works for these:
\\test\test$\TEST.xls
\\server\share\folder\myfile.txt
\\server\share\myfile.txt
\\123.123.123.123\share\folder\myfile.txt
c:\folder\myfile.txt
c:\folder\myfileWithoutExtension
Edit: Added example usage:
if (Regex.IsMatch (text, @"^(?:[a-zA-Z]\:|\\\\[\w\.]+\\[\w.$]+)\\(?:[\w]+\\)*\w([\w.])+$"))
{
// Valid
}
*Edit: * This is an approximation of the paths you could see. If possible, it is probably better to use the Path class or FileInfo class to see if a file or folder exists.