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%rs = (
    vdd  => 'P',
...
    vssa => 'G',
    vss  => 'G',
);

$line = "*.PIN foo:I bar:O vdd:I vssq:I vssa:O";
$line =~ s/\b(\w+):([A-Z])\b/$rs{$1} ? "$1:$rs{$1}" : "$1:$2"/eg;