Collen Zimba put Highlands in front after just nine minutes, firing home from close range after Richard Matloga had seen his spectacular shot rifling off the woodwork.
Zimba then fired a shot against the bar before Tshepo Lebetha netted Highlands’ second goal on 30 minutes, scoring from a throw-in routine.
It was 3-0 when Karabo Moses saw the ball skidding off his head and into his own goal, following a speculative Zimba drive.
Magesi pulled one goal back three minutes before the break when Tumelo Mashakana when on a scintillating solo run before hammering the ball past the Highlands Park keeper and inside the far post.
The Limpopo side started the second half with far more purpose, dominating possession and territory, and they pulled another goal back 20 minutes after the restart, Mashakana nodding home from close range; too little too late however to earn anything from the game.
After a tight opening to the game, All Stars took control of proceedings when Marawaan Bantam picked out the bottom corner of the net just before half time.
Five minutes after the restart Marcelino Johnson raced into the box and slotted home a clinical finish to double the advantage.
With 20 minutes left the Cape Town outfit scored their third when Amigo Memal got onto a through ball before steering an expertly touched volley beyond Molete and into goal.
Shining Stars (North West) v Angavu Stars
The final game of the day saw a 0-0 draw as Shining Stars and Angavu Stars failed to get the better of one another.
Chances were few and far between in the first half, although it was Angavu keeper Eziel Mamatela who was the busier of the two shot stoppers, having to deal with several dangerous aerial balls into the box.
Mamatela also made a great save to keep out a powerful shot from Thabo Schalk, while at the other end, Sinle Myeza missed a good chance when he blasted over from close range.
Mamatela was again called into the action just after the restart, making a brave block at the feet of Katlego Lentswe to keep his side in the game.
Both sides had their chances to grab all three points, with the Eastern Cape aside coming closest when Simlindile Zuka’s added time header hit the woodwork.
The action continues on Wednesday, with matches scheduled for the following times at the SJ Smith Stadium in Lamontville, Durban:
Day 2 (Wednesday, 23 July 2014 - SJ Smith Stadium)
09H00: Cape Town All Stars v Angavu Stars
11H00: Magesi FC v Natal United/ Kings United
13H00: Shining Stars v Apollo / Phiva Young Stars (Eastern Cape)
15H00: Steach United v Highlands Park
Day 3 (Thursday, 24 July 2014 - King Zwelithini Stadium)
11H00: Highlands Park v Natal United/ Kings United
11H00: Steach United v Magesi FC
14H00: Angavu Stars v Sibanye Golden Stars
14H00: Apollo / Phiva Young Stars v Cape Town All Stars
Day 4 (Friday, 25 July 2014 - King Zwelithini Stadium)
13H00: Cape Town All Stars v Shining Stars
13H00: Apollo / Phiva Young Stars v Sibanye Golden Stars
Day 5 (Saturday, 26 July - King Zwelithini Stadium)