I agree with Nance, yet again!!!...to start using your debit cards now. Use them at the grocery store and gas station so you are used to them when you travel. IF your bank has an ATM, try that a couple of times too just to get some cash and so you will be familiar with how they work. Of course they will be a bit different in Europe. And I ONLY use my debit card to get cash from an ATM in Europe. I do not use it for purchases.
I like to have Euro in my pocket when I arrive. You won't be jet-lagged but you'll need Euro for transportation to the train station from your dock and then a ticket to Haarlem (Nance will know for sure but I think this has to be by credit card). When I first started traveling to Europe I got about 100E from my bank before I left home. The exchange rate is not as good as if you were getting cash out of a European ATM but I needed that security. Now I just bring back money with me for my next trip.
I travel solo and I bring 2 credit cards and 2 debit cards (one on my local Credit Union and one from my Money Market) in case one of them is compromised.
When you are on the bus going from Cinque Terre to Switzerland your guide will help the group figure out how much each person will need in Swiss Francs. They may stop at a Swiss ATM for people to change money.
One thing I forgot is that if your guide offers optional things, take them up on it! Generally they will all offer to organize a gondola ride in Venice, but mine also offered a couple of extra meals. He ordered, we paid him and had a wonderful time. On the free day in Switzerland mine also offered to take anyone who wanted up to the top of the Schilthorn, then offered to take those who wanted up the opposite side of the valley to do an easy hike. Swiss transportation is expensive...don't blink, don't think about it, just do it!
Soap is provided everywhere so you don't need to bring this. Shampoo usually is as well altho I am sensitive to products so I bring my own shampoo and conditioner. If your wife has sensitivities to shampoos she may want to consider bringing small containers of shampoo and conditioner.
As far as packing....the best advice I got here when I first started is to "pack on paper first". Yep, do a packing list and stick to it. Probably for your wife more than you, have her do a capsule wardrobe where everything matches everything else. All pants match all shirts match all sweaters.
You'll sometimes have free time, especially in the bigger cities so if you forgot something you can shop for it.
Do bring small daypacks or a tote to use for a "bus bag". You can leave this on the bus and have your jacket/guidebook/water/snacks/entertainment in it. You'd not need to carry this in the cities on walking tours, etc. You can also use this bag to take your stuff for 2 nights in to Venice and Monterosso.
I try to get my suitcase down to 20# but the best I've done is 22#. There may be instances where you have to carry your cases upstairs as you will have to porter them yourselves so please don't burden yourselves with 49#! I'd do a trial pack then head for a trail in your area and see if you can manage this over at least 1/2 a mile. You shouldn't have to manage it that far but that will give you a fair assessment. I pack for up to 8 weeks in a 21 inch wheelie.
If your wife wants ideas on color combinations for capsule wardrobes, have her take a look at The Vivienne Files blog. She has wonderful ideas on colors altho many of her clothes are too expensive or too dressy for my N. Idaho lifestyle!
PS Also plan to keep a journal of some sort. Even if you just write a couple of lines a day or list your expenses you'll thank yourself at the end. Especially when you write your Trip Report to post here, lol!!