Both sides packed a significant punch going forward, but there was still plenty of entertainment on offer in a see-sawing encounter, with Sam Tomkins' try 11 minutes from time ultimately proving the difference.
There were two tries apiece in the first half, with Michael Shenton and Kallum Watkins crossing for England and Isaac Liu and Daniel Vidot scoring for Samoa, but it was England who led 14-10 at the break thanks to the boot of Gareth Widdop.
Samoa never stopped coming at their more fancied opponents, however, and actually led the game with 20 minutes remaining, but England never curbed their own attacking instincts and eventually prevailed.
Liam Farrell, Joel Tomkins and Sam Tomkins all grabbed four-pointers for England in the second half, while Samoa remained competitive with a try from Antonio Winterstein and a double from Pita Godinet.
It was England who opening the scoring after an intense opening 21 minutes when Daryl Clark put himself in the clear with a big right foot step before laying the ball on to Shenton to cruise over for a try.
Samoa were immediately back on the front foot with the assistance of a pair of penalties, and the pressure soon told as Liu bashed through a cluster of England tacklers to touch down under the posts.
Vidot gave the Pacific Islanders the lead with 10 minutes to go in the first half before a slick backline move that passed through the hands of Matty Smith and Sam Tomkins saw Watkins find himself with plenty of space to run into on the right edge and he cruised over.
Widdop made no mistake with a tough conversion to put England back in front and also added a penalty when Clark was manhandled in a tackle by Josh McGuire.
The momentum stayed with England after the interval and Widdop sent Farrell over with a sweet pass.
That gave England a 20-10 lead and left Samoa needing to score next to stay in the game; and Godinet duly obliged by throwing off the opposition defence with a massive dummy and scooting over the line.
The acting hooker scored an even more impressive try moments later when he darted out of dummy half to catch the English defence napping. Kyle Stanley did well to convert and Samoa edged in front 22-20 with a quarter of the match remaining.
England were awarded a controversial four-pointer when Joel Tomkins crossed after what appeared to be a knock-on before his brother Sam received a favourable call from the video referee again when he stretched over the line to plant the ball and extend the lead.
Even then, the match was not over, as Samoa struck back through winger Winterstein, who finished off a Hail Mary play by barging through two players, but England held on to record a crucial win to start their Four Nations campaign.