The lines of declination shown are isogonic, not directional. They don't show the direction to magnetic north, they link points where the angle between true north and magnetic north is the same.
In fact, the map (bottom) suggests that the Pacific actually has less magnetic declination than most places, only 0-20. It's really hard to judge where they are pointing, exactly, but it looked like more than 20 degrees off to me.
I also mistrust Jack's estimation of west -- even if he remembered accurately where the sun had gone down the night before, the sunset azimuth varies considerably with the season.
They are only three weeks off autumn equinox, though, so the sun should be nearly directly west. The producers have said the official crash date was the date of the series' American premiere. Your point about hikers misestimating a 90 degree turn is taken, but I think we are supposed to take this as a real strangeness. The annoying part was, Sayid never said whether he checked it against his homemade compass!
So there are lots of ways errors can creep in. I think the point of the whole bit is "This place is weird. Locke is weird. Don't trust either one."
Two things are reinforcing my distrust of Locke. One, a general increase in the dangerousness of his provocations: first one, he just says Jack shouldn't come with him and should go visionquesting. Now perhaps it wasn't the wisest idea ever to encourage the lone doctor to go haring off through the wilderness after hallucinations, but Jack had already started it and it's understandable that Locke would think it a great idea given his beliefs. He only gave Jack advice, he didn't do anything without his consent. Then next we have him using Charlie as boar bait. Pretty risky, and Charlie may have consented to a walk, but not being bait. Then we have him pointing Sayid at Sawyer, *and giving him a weapon*. He's moved on to using people as weapons. And now we have him physically assaulting Boone and tying him up in the wilderness.
Second, it's the weakest people in the group who are following him most devoutly, and he seems to be encouraging that. While two of the three people who might be expected to have the sharpest eye for hinkiness don't trust him. Kate, who is a conwoman, and Sayid, who served in the RG in Saddam's Iraq and has first hand experience with a cult of personality. It'd be interesting to hear Sawyer's opinion of Locke.