Kane produced two typically lethal finishes in the second half of the Nations League Group B2 tie at Wembley.
It was the perfect way for the Bayern Munich striker to celebrate becoming the 10th man to make 100 appearances for England.
The 31-year-old is England's all-time leading scorer with 68 and also set Tottenham's record goal-tally before joining Bayern.
But, despite all the plaudits thrown his way on the night he reached his England century, Kane still carries the hurt from a disappointing personal campaign at Euro 2024.
He scored three times in Germany but rarely impressed as England laboured through the tournament before losing to Spain in the final, leading to questions about whether he still deserved his place in the team.
Using that frustration as motivation, Kane was delighted to celebrate his 100th cap in style.
"It was a big night for me, really proud. I want to score goals and help the team. Whenever you are doubted, it makes you more hungry to prove people wrong," he said.
"We spoke about being ruthless but in these games you have to keep knocking on the door and you will get your reward.
"I always back myself to score goals and I'm excited for the future."
Golden cap
Kane was presented with a commemorative golden cap before kick-off, wore gold boots during the game and had his family in attendance to share in the latest highlight in his remarkable career.
The striker's success is a tribute to his perseverance, dating back to the start of his career when Tottenham sent him on loan to Millwall, Leyton Orient, Norwich and Leicester amid doubts about his ability to make it at the highest level.
Kane eventually proved his worth but even he conceded he would not have dared to dream about winning 100 caps at that time.
"I don't think I was even thinking of 100 caps when I was on loan at Millwall, Norwich and Leicester," he said.
"At that time it was about getting back into the Spurs team. I have always had a good self belief.
"I would for sure have been proud if I knew I was going to get 100 caps."
Saluting the influence of Mauricio Pochettino, the manager who gave him his chance at Tottenham, Kane said: "I have learned a lot over the years with Mauricio when he was at Spurs.
"The game is evolving a bit and it is great for me to keep learning."
England interim boss Lee Carsley has worked with Kane for only a week in his first matches since replacing Gareth Southgate on a temporary basis.
But the 50-year-old has already begun to understand the ferocious drive that makes Kane such a prolific goal-scorer.
"Harry took his goals really well, a big occasion for him. Kids being here, an emotional night, but really happy for Harry. He fully deserves all the plaudits," he said.
"What I have noticed this week is he is highly motivated to play for England and score goals and to have a centre forward like that, hopefully it continues."
Kane's golden evening had just one blemish when his youngest son burst into tears just before the striker and his children were due to lead the team out.
But even that couldn't spoil one of the striker's most unforgettable days.
"My son was having a bit of a meltdown. It was past his bedtime, thankfully my wife was there to look after him," Kane said.
