Congratulations. On the B4s, the story is:
If you are a returning Canadian, you get to fill out one B4/B4A set that will allow you to import goods duty free as long as you've been out of Canada for at least one year and have owned, used, and possessed the items for at least 6 months (6 month req't waived if you've been out of Canada for five years). If you are importing any item over 10,000 Canadian you will have to pay duties on the amount over 10k. The government gives you one opportunity to tell them what you are bringing in so you need to fill out all the forms upfront and then you can bring it in over time but be sure to include everything upfront.
Similarly, your wife, as an immigrant can fill out one B4/B4A set which she has to turn in on her first visit where she intends to live in Canada more than 12 months. She does not have the 10k limit per item.
As for filling out the forms, you can group like items together - eg clothes $xxxx if the value isn't huge or you can break it down a bit to say suits $xxxx, formal gowns $xxx, casual clothes $xxx. Same for lower value items like household goods, toiletries, etc. If you eat importing thing over several trips (or on plane ve shipment), try to separate line items per trip so that you don't run into issues when they cross items off as you import them.
For jewelry and electronics, you need to list them one per line item and include: for jewelry a photo (can be one you took yourself and printed) - don't forget wedding bands! - and for electronics you should include model and serial number. You may also want to take photos of furniture if you aren't importing t immediately. You can complete multiple B4A forms and just number them. Folks have also reported using other formats (Excel, packing lists) successfully.
If you can take an extra copy, it will make life easier for you and the CBSA agent since they keep one and give one (once stamped) back to you.
The B4 is available at http://www.cbsa-asfc.gc.ca/publications/forms-formulaires/b4-eng.pdf
And the B4A is at http://www.cbsa-asfc.gc.ca/E/pbg/cf/b4a/
Detailed instructions are at http://cbsa-asfc.gc.ca/publications/pub/bsf5113-eng.html
Are you importing a car? If so, there's a few more detailed instructions so I'll dig for some posts where I summarized things to consider.
