That won't work
The first method works because Buff2 is a pointer to the Buff2 array so adding 6 to it adds 6 to the address and it points to a starting point later in the array. However, Buff2[6] is a single character in the array so the comparison fails
However, this works
void setup()
{
Serial.begin(115200);
char Buff1[30] = "abcdefghijklmnopqrst";
char Buff2[30] = "123456abcdefghijklmnopqrst";
if (strcmp(Buff1, &Buff2[6]) == 0)
{
Serial.println("COMPARE TRUE");
}
else
{
Serial.println("COMPARE FALSE");
}
}
void loop()
{
}
because the ampersand means "address of" rather than "value of"