# you can get rid of the ($netHash{$val} > 1.0) test
# I only included it to make the example more like yours
   if($netHash{$val} > 1.0 && $netHash{$val} < 1.4) {
         my ($x1, $y1) = ($val,$netHash{$val});
         $capVal_1_Hash{$x1} = $y1;
   }
   elsif($netHash{$val} > 1.4 && $netHash{$val} < 1.9) {
         my ($x2, $y2) = ($val,$netHash{$val});
         $capVal_2_Hash{$x2} = $y2;
   }
   ...
   ...

##</code><code>##

sub printHash {
    my $href = shift;
    my @href_keys = keys %{$href};
    my $RandKey = $href_keys[int(rand(scalar @href_keys))];
    print "$RandKey $href->{$RandKey}\n";
}

##</code><code>##

foreach my $n ( 1 .. 100 ) {
    printHash( $capVal_hash{$n} );
}

##</code><code>##

my @range_destination
    = ( [  1.0,   1.4,   1 ],
        [  1.4,   1.9,   2 ],
        ...
        [ 99.2,  99.8,  99 ],
        [100.1, 100.9, 100 ],
       );

# what you call $val is really a KEY,
# but I'll keep your name anyway.
while ( my ( $val, $real_val ) = each %netHash ) {
  CONDITION:
    foreach my $cond_ref ( @range_destination ) {
        my ( $min, $max, $dest ) = @$cond_ref;
        if ( $val > $min && $val < $max ) {
            $capVal_Hash{$dest}{$val} = $real_val;
            last CONDITION;
        }
    }
}