Update: Oops, i actually meant to say: Is there anyway to do this same thing on the values of a hash?

Do you mean just the values themselves or the keys based on the values? Here is some code for both cases:

my %hash = (
    4 => 20,    # second highest key
    2 => 40,    # second highest value
    3 => 30,
    1 => 50,
    5 => 10,
);

# second highest value
print ((sort values %hash)[-2]);

# key based on the second highest value
print ((sort { $hash{$b} <=> $hash{$a} } keys %hash)[1]);
[download]

L-LL-L--L-LL-L--L-LL-L--
-R--R-RR-R--R-RR-R--R-RR
B--B--B--B--B--B--B--B--
H---H---H---H---H---H---
(the triplet paradiddle with high-hat)