The non-greedy *? is perfectly happy to eat up nothing unless you tell it how far to go. So either use the greedy version for the second capture or anchor with, say, $. Try either of these:

print "$1 $2\n" if($str=~/(.*?)\*(.*)/);
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print "$1 $2\n" if($str=~/(.*?)\*(.*?)$/);
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Note that both of them produce:

Test .Value
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Elimination of that . left as an exercise. ;-)