〜上に
on top of, besides, in addition
Plain form + 上に (な-adj + な · Noun + の / である)
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上に adds a second point of the same kind to the first: この部屋は広い上に、駅から近い, "this room is spacious, and on top of that it's close to the station".
Both halves go in the same direction: good plus good, or bad plus bad. 道に迷った上に、雨まで降ってきた, "I got lost, and on top of that it started raining".
It follows a plain form; な-adjectives take な (親切な上に), and nouns take の or である.
Don't confuse it with 上で ("after, based on") or 上は ("now that"). Compare し (N4), which lists reasons more loosely, and に加えて, which adds nouns.
Examples
この部屋は広い上に、駅から近い。
This room is spacious, and on top of that it's close to the station.
道に迷った上に、雨まで降ってきた。
I got lost, and on top of that it started raining.
彼女は頭がいい上に、性格もいい。
She's clever, and she has a lovely personality too.
この仕事は給料が安い上に、休みも少ない。
This job pays badly, and there's hardly any time off either.
親切な上に、仕事も早い。
They're kind, and they work fast too.