Dependent Care Account/ Day Care Spending Account

No you can't. But contrary to what someone posted below, after school care absolutely applies and we put in for it every year.

And those of is with more than one qualifying child use the dependent care account and the child care tax credit together - basically you'll max out the dependent care account's tax advantages at $5K but because you have 2 kids and are eligible for up to $6K under the child care tax credit, the extra $1K in expenses (from $5K to $6K) would be eligible for the child care tax credit. Any basic tax software or accountant would be able to enter those amounts pretty easily.

At the end of the day, it isn't much of a savings but every little bit helps!

Here's what this link said:

The cap is $5,000 for single heads of household or folks who are married and filing jointly. Here are some other aspects of flex spending accounts to consider:

You must open a Dependent Care Flexible Spending Account during the annual enrollment period. To make any changes to the amount you're having deducted, or to enroll outside of that window, you'll have to meet the criteria for a "qualifying event." Check with your HR representative to find out if you qualify.
Unlike a health-care flexible spending plan, you cannot get reimbursed for an expense that is greater than the amount you currently have set aside in your account.
Flex spending plans work under the "use it or lose it" principle, which means that if you haven't spent the total amount by the deadline and requested reimbursement, you can say goodbye to the money. Therefore, your calculations to determine how much to set aside need to be as accurate as possible.

Child-care tax credit
The Child-Care Tax Credit allows you to apply up to $3,000 of expenses paid in a year for one qualifying individual, or $6,000 for two or more qualifying individuals, to your taxes through the Dependent-Care Tax Credit. In order to claim the credit, you must fill out Form 2441: Child and Dependent-Care Expenses (opens a PDF) when you file your federal return.

To take the Child Care Tax Credit, you don't have to fill out any enrollment forms or have money taken out of your paycheck. You do have to file your federal tax return by the IRS deadline, however.
The "use it or lose it" rule doesn't apply, since none of your money has been taken from your paycheck outright.
Since the amount of the credit is based on your adjusted gross income, folks in higher tax brackets may be able to save more under the flex spending program.

Which one should I choose?
The answer to this question depends entirely on your family's adjusted gross income, your tax bracket, and how many dependents you have. Take a look at this worksheet designed to help figure out which benefit will save you the most money, then check with your tax advisor to see what works best for your particular situation.

http://www.fool.com/investing/general/save-big-with-depen...

You can also talk to the IRS and ask them as well.

http://www.irs.gov/uac/Telephone-Assistance

No, the only way you could both do it is if you were married filing single and by doing that it would cost you much more than the deduction saves you.

Nope, wish I could too!

However, you can use the $5000 flex plan for one child in daycare, and when tax times comes, you can claim the child care tax credit for the other child in daycare.

Neither applies to aftercare expenses once your child is in school.