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Deuteronomy 29:5-6 NASB

5 I have led you forty years in the wilderness; your clothes have not worn out on you, and your sandal has not worn out on your foot. 6 You have not eaten bread, nor have you drunk wine or strong drink, in order that you might know that I am the Lord your God.

But years back when they had complained about bread and meat God had given them Manna and Quial.

Exodus 16:4-5 NASB

4 Then the Lord said to Moses, “Behold, I will rain bread from heaven for you; and the people shall go out and gather a day’s portion every day, that I may test them, whether or not they will walk in My [b]instruction. 5 On the sixth day, when they prepare what they bring in, it will be twice as much as they gather daily.

Nehemiah 9:14, 15 NASB

14“So You made known to them Your holy sabbath,
And laid down for them commandments, statutes and law,
Through Your servant Moses 15
“You provided bread from heaven for them for their hunger,
You brought forth water from a rock for them for their thirst,
And You told them to enter in order to possess
The land which You [e]swore to give them.

Its clear from the above texts that they had bread from heaven so why then does Deuteronomy say they didn't eat bread?

The manna is called לֶחֶם, which can mean bread, but also refers to any meal: for example, the daily sacrifice of meat is also לֶחֶם (Numbers 28:2). So when the manna is called לֶחֶם (Exodus 16:4, etc.), it doesn't mean it was actual bread. In this case, we are told explicitly that it was not actual bread.

When the layer of dew lifted, there on the surface of the wilderness was a fine flaky substance, as fine as frost on the ground.

The house of Israel called it manna; it was like coriander seed, white, and the taste of it was like wafers made with honey. (Exodus 16:15,31, NRSV)

The verses that say the Children of Israel ate bread are not interested in contrasting this unusual food with ordinary bread (i.e., the Children of Israel ate manna as opposed to bread), and in fact the manna is the fulfillment of God's promise to deliver bread/לֶחֶם from heaven (Exodus 16:4).

On the other hand, Deuteronomy does contrast manna, the heavenly food, with bread. In Deuteronomy 8:3 the meaning of the manna is explained as being to teach that a person doesn't live on bread alone.

He humbled you by letting you hunger, then by feeding you with manna, with which neither you nor your ancestors were acquainted, in order to make you understand that one does not live by bread alone, but by every word that comes from the mouth of the Lord.

Of course, this verse would be unintelligible if both the manna and actual bread were referred to here by the same word.

Deuteronomy 29:6 doesn't explicitly contrast manna with bread, but it recalls Deuteronomy 8:3 which does, and therefore Moses also says that they didn't eat bread there with the same meaning: they didn't eat regular bread but rather the heavenly manna.