For The First Time, First Time
adverb, の adjective
You know that 初 means "first" This word means for the first time. Think of めて as "meet." Then think "when we met for the first time ____ happened."
はじめて
This word uses the kun'yomi, which you didn't learn with the kanji, so here's a mnemonic to help you out. What are you beginning? You are beginning Haj (はじ). (Haj is the fifth pillar of Islam, and is a pilgrimage to Mecca during the month of Dhu al-Hijja).
日本は初めてですか？
Is this your first time in Japan?
初めてのことばかりで、四苦八苦しています。
I'm struggling with all these new experiences.
初めて会った時から、ずっと気になっていました。
I've been interested in you since the first time we met.