Ah yes, The Talk! About Not Being Taken For Granted and treated as an unpaid round-the-clock chambermaid/restaurant/butler service. Sounds very familiar. He is being unreasonable.
Actually you already have one bargaining chip - you are doing his bookkeeping for free. How about stopping it altogether and saying you won't do it until he changes his attitude? Or start charging him for your work. 
If he still won't budge, there are 2 options -1) use those 2 hours that your DS is at nursery as your "clocking off" time, and do the housework when everyone is home. Or 2) as others have mentioned, you clock off in the evening as soon as dinner is served. Others are clocking off, you clock off too.
Here's another bit about chores: your DH has to start doing some stuff, even if it's only loading the dishwasher at night and some things at the weekends like mowing the loan and some of the hoovering. Tell your DH he has to do some chores to set a GOOD EXAMPLE to his kids. He doesn't want to be remembered as the dad whose kids say "well, I have no idea what he does at work but he just dosses about at home".
Your eldest needs to start doing some chores too - eg putting out own clothes, making own bed and helping to set the table and helping bring dirty dishes into the sink/kitchen for Dad to put into dishwasher (I don't know what the layout of your home is like). Any child over 7 should have a certain number of small chores so that they can grow up with some self respect and not be one of "those" who you see in the first year of college living away from home who have no idea how to look after themselves. Your five year old can help put away toys and "direct" the three year old to do some - little kids are love to boss their younger siblings and are actually quite effective at doing getting younger siblings to do tasks.
I have often seen a direct correlation between children doing chores and higher self esteem, more confidence and better school results (if there is no tutoring involved) - I see so many children of people I know who get waited hand and foot by their mums who don't feel capable of doing anything that they haven't been spoonfed. And all the highest achieving classmates I had in school did chores - and were proud of what they were able to do.
You need to apply for a debit card -seriously! How do you withdraw money from a cash till? If you don't have a current account, apply for one just to be used as a clearing account. But for internet shopping, you must use your husband's credit card - either get him to put you on it as a joint card holder or use his details to pay. If he goes on and on about money being so important, I can't imagine how he is letting you pay for groceries day in day out with cash - think of all the reward points and cashback the household is losing. And also credit card purchases come with replacement guarantees, which cash doesn't, if an item should prove faulty that the shop won't change. They've actually found that it is greener to use an internet delivery service rather than driving to a supermarket (unless you live right next to it) - and you can also surf for bargains and reserve them. I do internet grocery shopping because 1) it works out far cheaper than walking into a supermarket for the same items, 2) it saves on petrol - my nearest supermarket is quite some distance away, 3) it saves time and hassle, esp when it's raining.
There is that perennial excuse that these men give - "I work all day so I get to relax when I come home". You don't hear working mothers (even those with SAHD husbands) saying that, I never have. I know of working mums whose hours are longer than what your DH does (full day, and then some evening and weekend shifts on top of that) who don't say "I'm entitled to relax" but who come back and say, "right, what else needs doing?" and get on and do it.
Good luck, I hope your second talk succeeds. Taking a spouse for granted is not a good way for him to treat his marriage.