The phrase can express regret or acceptance of limitations despite good intentions. With the best will in the world, I couldn't mend your broken vase—it was too shattered.
Pro Tip 2/3
Not Literal
The phrase is not about actual 'willpower' but about acknowledging sincere efforts or desires. With the best will in the world, we can't control the weather for your wedding.
Pro Tip 3/3
Phrase Flexibility
You can use the phrase in various positions in a sentence, not just at the start. I might, with the best will in the world, fail to live up to your expectations.