Just make your hash table values the arrays, and accumulate the values to them directly:
$Sites = 'CO','NE','IA'
$hshSite = @{}
Foreach ($Site in $Sites){$hshSite[$Site] = @()}
ForEach ($x in $csv)
{
$hshSite[$x.location] += <whatever it is your adding>
}
If there's a lot of entries in the csv, you might consider creating those values as arraylists instead of arrays.
$Sites = 'CO','NE','IA'
$hshSite = @{}
Foreach ($Site in $Sites){ $hshSite[$Site] = New-Object Collections.Arraylist }
ForEach ($x in $csv)
{
$hshSite[$x.location].add('<whatever it is your adding>') > $nul
}