I suspect it's actually working but that my use of system("printenv") to check my settings is incorrect. I've tried system("set") and system("env") with no luck. Suggestions? 
my %hash;
$hash{APP_DIR} = "/usr/vendor/app/version/";
$hash{TMP_DIR} = "/usr/tmp/";
$hash{PROJ_DIR} = "/usr/people/userid/app/";
$hash{APP_LOCATION} = "/usr/vendor/app/version/bin/";

...

use Env qw(keys %hash);

foreach $key (keys %hash) {
    eval("$key=\"$hash{$key}\"");
    print "  $key=$hash{$key}\n";
}

system("printenv");

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In reply to setting env vars from hash fails for me by ccarden

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