A few minor comments:

1. For clarity, why not call this 'macaddr' instead of 'chaddr'? (Same for my $chaddr, etc.)

      chaddr => 'XX:XX:XX:XX:XX:XX', # MAC Address of sending interface
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2. sleep 5; # wait for 5..., etc. is obvious. How about:

      sleep 5;  # allow capture process to establish
      sleep 10; # allow capture
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3. In this sequence, you don't need two arrays, and you can simplify a couple things:

      #my @macaddr = split(/:/, $chaddr);
      my @chaddr = split(/:/, $chaddr);
   
      #push(@macaddr, 0) for (1..10);
      push(@chaddr,(0)x10);
   
      #my @chaddr = map { hex($_) } @macaddr; 
      @chaddr = map { hex } @chaddr;
   
      # or combined, using the clearer(?) @macaddr:
      @macaddr = map { hex } (split/:/,'10:FF:2B:40:8C:FE'), (0)x10;
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4. You are modifying $i throughout this loop! In fact, you have a comment (# i = 0) that is certainly untrue the first pass, and may never be true.

       for (my $i = 0; $i <= $#options; $i++) {
           my $option = hex($options[$i++]);
           last if ($option == 255); # end of DHCP Options
           my $length = $options[$i++]; # i = 0
           my $offset = hex($length) + $i;
           for (my $k = $i; $k <= ($offset - 1); $k++ ) {
               push(@{$opts{$option}}, $options[$k]);
           }
            $i = $offset - 1;
        }
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5. A thought on printing:

        for my $key (keys %opts) {
            print $key, " ", dhcp_option($key),"\t";
            if (ref($opts{$key}) =~ m/ARRAY/) {
                print $_, " " foreach (@{$opts{$key}});
            }
            # NOTE: elsif can just be else, as a string
            # necessarily does or does not match /ARRAY/
            elsif (ref($opts{$key}) !~ /ARRAY/) {
                print $opts{$key};
            }
            print "\n";
        }
   
        # OR (untested):
    
        for my $key (keys %opts) {
            print "$key ", dhcp_option($key), "\t",
                  ( ref($opts{$key}) =~ /ARRAY/  
                       ? join" ", @{$opts{$key}} 
                       : $opts{$key}
                  )
                  "\n";
        }
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