If you know someone who can build amps then they absolutely could sort you out. If it's what I think it is, it's a simple fix for someone who has a little electronics experience.
To answer you questions though.
Yes, a low rumble type noise is almost certainly hum from mains power whether it's 50Hz or 60Hz. Obviously the sound would be slightly higher in pitch for 60Hz, but the cause and cure are the same regardless.
You are right about pretty much everything else as well. A cap is indeed a condenser, I just thought "condenser" was a really old word, not a geographically variable term. You know, like "Wireless" Vs "Radio" rather than "valve" Vs "tube", but there you go, I learnt something new
Electrolytic caps are indeed the barrel shaped ones, and the type you would use would have a "-" and a "+" with the "+" going to the 5V and the "-" to ground. It matters a lot which way they are connected, just like a diode or a transistor. The wrong way and they fry. In fact its really easy to make them explode if you have enough voltage to play with, but with 5V nothing is going to go boom, it just wont work.
As to cap value, honestly I'd use whatever I found in my junk box that was over 10uF and rated at 16V or above. 100uF or even 470uF might be good to try actually, but there's likely a wide range of values that'd fix it up. Just FYI though, using a -very- high value cap you run the risk of killing the power supply as it tries to quickly charge the cap when it's turned on, a phenomenon called "surge current".
There is a complex formula (and by "complex" I mean, I cant think of it off the top of my head right now) to determine the exact amount of capacitance needed to squash ripple (hum) in a power supply, but that's only really worth bothering about if you are designing a power supply that cranks out many amps, not a little 5v brick. You'd also need to know if the power supply was bridge rectified or not, and to figure that out without pulling it apart you'd need a scope and bleh, too much hassle.
Lastly, all polarized caps are marked, so thats easy, no need for a meter there.
But as I said at the start, any amp tech knows how to fix this and it's not a big deal for them. A well filtered 5V brick as a replacement is not a bad idea, but I suspect they will be slightly rarer than 9V ones.
Oh and one last thing. All that assumes the power supply is 5VDC. If it's 5VAC then you'll need to hack the pedal itself. The power supply should have that written on it really 5VDC or 5VAC.
Oh and to satisfy my burning curiosity, what kind of pedal will run on 5V?
Oh and lastly.... I wrote a bit of a thing on caps for someone else over
HERE if you want to read more..